50 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
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
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
Exploring Barriers and Opportunities in Adopting Crowdsourcing Based New Product Development in Manufacturing SMEs
Crowdsourcing is an innovative business practice of obtaining needed services, ideas, or content or even funds by soliciting contributions from a large group of people (the ‘Crowd’). The potential benefits of utilizing crowdsourcing in product design are well-documented, but little research exists on what are the barriers and opportunities in adopting crowdsourcing in new product development (NPD) of manufacturing SMEs. In order to answer the above questions, a Proof of Market study is carried out on crowdsourcing-based product design under an Innovate UK funded Smart project, which aims at identifying the needs, challenges and future development opportunities associated with adopting crowdsourcing strategies for NPD. The research findings from this study are reported here and can be used to guide future development of crowdsourcing-based collaborative design methods and tools and provide some practical references for industry to adopt this new and emerging collaborative design method in their business
A new class of glycomimetic drugs to prevent free fatty acid-induced endothelial dysfunction
Background: Carbohydrates play a major role in cell signaling in many biological processes. We have developed a set of glycomimetic drugs that mimic the structure of carbohydrates and represent a novel source of therapeutics for endothelial dysfunction, a key initiating factor in cardiovascular complications. Purpose: Our objective was to determine the protective effects of small molecule glycomimetics against free fatty acidinduced endothelial dysfunction, focusing on nitric oxide (NO) and oxidative stress pathways. Methods: Four glycomimetics were synthesized by the stepwise transformation of 2,5dihydroxybenzoic acid to a range of 2,5substituted benzoic acid derivatives, incorporating the key sulfate groups to mimic the interactions of heparan sulfate. Endothelial function was assessed using acetylcholineinduced, endotheliumdependent relaxation in mouse thoracic aortic rings using wire myography. Human umbilical vein endothelial cell (HUVEC) behavior was evaluated in the presence or absence of the free fatty acid, palmitate, with or without glycomimetics (1µM). DAF2 and H2DCFDA assays were used to determine nitric oxide (NO) and reactive oxygen species (ROS) production, respectively. Lipid peroxidation colorimetric and antioxidant enzyme activity assays were also carried out. RTPCR and western blotting were utilized to measure Akt, eNOS, Nrf2, NQO1 and HO1 expression. Results: Ex vivo endotheliumdependent relaxation was significantly improved by the glycomimetics under palmitateinduced oxidative stress. In vitro studies showed that the glycomimetics protected HUVECs against the palmitateinduced oxidative stress and enhanced NO production. We demonstrate that the protective effects of preincubation with glycomimetics occurred via upregulation of Akt/eNOS signaling, activation of the Nrf2/ARE pathway, and suppression of ROSinduced lipid peroxidation. Conclusion: We have developed a novel set of small molecule glycomimetics that protect against free fatty acidinduced endothelial dysfunction and thus, represent a new category of therapeutic drugs to target endothelial damage, the first line of defense against cardiovascular disease