206 research outputs found
Interference enhanced thermoelectricity in quinoid type structures
Quantum interference (QI) effects in molecular junctions may be used to
obtain large thermoelectric responses. We study the electrical conductance G
and the thermoelec- tric response of a series of molecules featuring a quinoid
core using density functional theory (DFT), as well as a semi-empirical
interacting model Hamiltonian describing the {\pi}-system of the molecule which
we treat in the GW approximation. Molecules with a quinoid type structure are
shown to have two distinct destructive QI features close to the frontier
orbital energies. These manifest themselves as two dips in the transmission,
that remain separated, even when either electron donating or withdraw- ing side
groups are added. We find that the position of the dips in the transmission and
the frontier molecular levels can be chemically controlled by varying the
electron donating or withdrawing character of the side groups as well as the
conjugation length inside the molecule. This feature results in a very high
thermoelectric power factor S^2G and figure of merit ZT, where S is the Seebeck
coefficient, making quinoid type molecules potential candidates for efficient
thermoelectric devices.Comment: 22 pages, 11 figure
Image effects in transport at metal-molecule interfaces
We present a method for incorporating image-charge effects into the
description of charge transport through molecular devices. A simple model
allows us to calculate the adjustment of the transport levels, due to the
polarization of the electrodes as charge is added to and removed from the
molecule. For this, we use the charge distributions of the molecule between two
metal electrodes in several charge states, rather than in gas phase, as
obtained from a density-functional theory-based transport code. This enables us
to efficiently model level shifts and gap renormalization caused by
image-charge effects, which are essential for understanding molecular transport
experiments. We apply the method to benzene di-amine molecules and compare our
results with the standard approach based on gas phase charges. Finally, we give
a detailed account of the application of our approach to porphyrin-derivative
devices recently studied experimentally by Perrin et al. [Nat. Nanotechnol. 8,
282 (2013)], which demonstrates the importance of accounting for image-charge
effects when modeling transport through molecular junctions
Deltas in dialogue: Imagining policy transfer from the Netherlands to Vietnam and Bangladesh as a symmetrical conversation
Large tunable image-charge effects in single-molecule junctions
The characteristics of molecular electronic devices are critically determined
by metal-organic interfaces, which influence the arrangement of the orbital
levels that participate in charge transport. Studies on self-assembled
monolayers (SAMs) show (molecule-dependent) level shifts as well as
transport-gap renormalization, suggesting that polarization effects in the
metal substrate play a key role in the level alignment with respect to the
metal's Fermi energy. Here, we provide direct evidence for an electrode-induced
gap renormalization in single-molecule junctions. We study charge transport in
single porphyrin-type molecules using electrically gateable break junctions. In
this set-up, the position of the occupied and unoccupied levels can be followed
in situ and with simultaneous mechanical control. When increasing the electrode
separation, we observe a substantial increase in the transport gap with level
shifts as high as several hundreds of meV for displacements of a few \aa
ngstroms. Analysis of this large and tunable gap renormalization with
image-charge calculations based on atomic charges obtained from density
functional theory confirms and clarifies the dominant role of image-charge
effects in single-molecule junctions
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Enantio- and diastereoselective synthesis of γ-amino alcohols
The γ-amino alcohol structural motif is often encountered in drugs and natural products. We developed two complementary catalytic diastereoselective methods for the synthesis of N-PMP-protected γ-amino alcohols from the corresponding ketones. The anti-products were obtained through Ir-catalyzed asymmetric transfer hydrogenation, the syn-products via Rh-catalyzed asymmetric hydrogenation
Evaluation of the zucker diabetic fatty (ZDF) rat as a model for human disease based on urinary peptidomic profiles
Representative animal models for diabetes-associated vascular complications are extremely relevant in assessing potential therapeutic drugs. While several rodent models for type 2 diabetes (T2D) are available, their relevance in recapitulating renal and cardiovascular features of diabetes in man is not entirely clear. Here we evaluate at the molecular level the similarity between Zucker diabetic fatty (ZDF) rats, as a model of T2D-associated vascular complications, and human disease by urinary proteome analysis. Urine analysis of ZDF rats at early and late stages of disease compared to age- matched LEAN rats identified 180 peptides as potentially associated with diabetes complications. Overlaps with human chronic kidney disease (CKD) and cardiovascular disease (CVD) biomarkers were observed, corresponding to proteins marking kidney damage (eg albumin, alpha-1 antitrypsin) or related to disease development (collagen). Concordance in regulation of these peptides in rats versus humans was more pronounced in the CVD compared to the CKD panels. In addition, disease-associated predicted protease activities in ZDF rats showed higher similarities to the predicted activities in human CVD. Based on urinary peptidomic analysis, the ZDF rat model displays similarity to human CVD but might not be the most appropriate model to display human CKD on a molecular level
First report of generalized face processing difficulties in möbius sequence.
Reverse simulation models of facial expression recognition suggest that we recognize the emotions of others by running implicit motor programmes responsible for the production of that expression. Previous work has tested this theory by examining facial expression recognition in participants with Möbius sequence, a condition characterized by congenital bilateral facial paralysis. However, a mixed pattern of findings has emerged, and it has not yet been tested whether these individuals can imagine facial expressions, a process also hypothesized to be underpinned by proprioceptive feedback from the face. We investigated this issue by examining expression recognition and imagery in six participants with Möbius sequence, and also carried out tests assessing facial identity and object recognition, as well as basic visual processing. While five of the six participants presented with expression recognition impairments, only one was impaired at the imagery of facial expressions. Further, five participants presented with other difficulties in the recognition of facial identity or objects, or in lower-level visual processing. We discuss the implications of our findings for the reverse simulation model, and suggest that facial identity recognition impairments may be more severe in the condition than has previously been noted
Structural versus Electrical Functionalization of Oligo(phenyleneethynylene) Diamine Molecular Junctions
We explore both experimentally and theoretically the conductance and packing of molecular junctions based on oligo(phenyleneethynylene) (OPE) diamine wires, when a series of functional groups are incorporated into the wires. Using the scanning tunnelling microscopy break-junction (STM BJ) technique, we study these compounds in two environments (air and 1,2,4-trichlorobenzene) and explore different starting molecular concentrations. We show that the electrical conductance of the molecular junctions exhibits variations among different compounds, which are significant at standard concentrations but become unimportant when working at a low enough concentration. This shows that the main effect of the functional groups is to affect the packing of the molecular wires, rather than to modify their electrical properties. Our theoretical calculations consistently predict no significant changes in the conductance of the wires due to the electronic structure of the functional groups, although their ability to hinder ring rotations within the OPE backbone can lead to higher conductances at higher packing densities
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