Project description:Metalloproteins, proteins containing a transition metal ion cofactor, are electron transfer agents that perform key functions in cells. Inspired by this fact, electron transport across these proteins has been widely studied in solid-state settings, triggering the interest in examining potential use of proteins as building blocks in bioelectronic devices. Here, we report results of low-temperature (10 K) electron transport measurements via monolayer junctions based on the blue copper protein azurin (Az), which strongly suggest quantum tunneling of electrons as the dominant charge transport mechanism. Specifically, we show that, weakening the protein-electrode coupling by introducing a spacer, one can switch the electron transport from off-resonant to resonant tunneling. This is a consequence of reducing the electrode's perturbation of the Cu(II)-localized electronic state, a pattern that has not been observed before in protein-based junctions. Moreover, we identify vibronic features of the Cu(II) coordination sphere in transport characteristics that show directly the active role of the metal ion in resonance tunneling. Our results illustrate how quantum mechanical effects may dominate electron transport via protein-based junctions.
Project description:In this article, we have investigated the influence of the nitro side-group on the single molecular conductance of pyridine-based molecules by scanning tunneling microscopy break junction. Single molecular conductance of 4,4'-bipyridine (BPY), 3-nitro-4-(pyridin-4-yl)pyridine (BPY-N), and 3-nitro-4-(3-nitropyridin-4-yl)pyridine (BPY-2N) were measured by contact with Au electrodes. For the BPY molecular junction, two sets of conductance were found with values around 10-3.1 G? (high G) and 10-3.7 G? (low G). The addition of nitro side-group(s) onto the pyridine ring resulted in lower conductance of 10-3.8 G? for BPY-N and 10-3.9 G? for BPY-2N, respectively, which can be attributed to the twist angle of two pyridine rings. Moreover, the steric hindrance of nitro group(s) also affects the contacting configuration of electrode-molecule-electrode. As a consequence, only one set of conductance value was observed for BPY-N and BPY-2N. Our work clearly shows the important role of side-groups on the electron transport of single-molecule junctions.
Project description:Semiconducting molybdenum disulfphide has emerged as an attractive material for novel nanoscale optoelectronic devices due to its reduced dimensionality and large direct bandgap. Since optoelectronic devices require electron-hole generation/recombination, it is important to be able to fabricate ambipolar transistors to investigate charge transport both in the conduction band and in the valence band. Although n-type transistor operation for single-layer and few-layer MoS2 with gold source and drain contacts was recently demonstrated, transport in the valence band has been elusive for solid-state devices. Here we show that a multi-layer MoS2 channel can be hole-doped by palladium contacts, yielding MoS2 p-type transistors. When two different materials are used for the source and drain contacts, for example hole-doping Pd and electron-doping Au, the Schottky junctions formed at the MoS2 contacts produce a clear photovoltaic effect.
Project description:Although tumor growth requires the mitochondrial electron transport chain (ETC), the relative contribution of Complex I (CI) and II (CII), the gatekeepers for initiating electron flow, remains unclear. Here, we report that loss of CII, but not CI, reduces melanoma tumor growth by increasing antigen presentation and T cell-mediated killing. This is driven by succinate-mediated transcriptional and epigenetic activation of major histocompatibility complex I-antigen processing and presentation (MHC-APP) genes that is independent of interferon signaling. Furthermore, knock-out of MCJ, to promote electron entry preferentially via CI, provides proof-of-concept of ETC rewiring to achieve anti-tumor responses without side effects associated with an overall reduction in mitochondrial respiration in non-cancer cells. Our results hold therapeutic potential for tumors that have reduced MHC-APP expression, a common mechanism of cancer immunoevasion.
Project description:We report on a theoretical study of spin-dependent electron transport through single-helical molecules connected by two nonmagnetic electrodes, and explain the experiment of significant spin-selective phenomenon observed in ?-helical protein and the contradictory results between the protein and single-stranded DNA. Our results reveal that the ?-helical protein is an efficient spin filter and the spin polarization is robust against the disorder. These results are in excellent agreement with recent experiments [Mishra D, et al. (2013) Proc Natl Acad Sci USA 110(37):14872-14876; Göhler B, et al. (2011) Science 331(6019):894-897] and may facilitate engineering of chiral-based spintronic devices.
Project description:The NLRP3 inflammasome is linked to sterile and pathogen-dependent inflammation, and its dysregulation underlies many chronic diseases. Mitochondria have been implicated as regulators of NLRP3 inflammasome through multiple mechanisms including generation of mitochondrial ROS. Here we report that mitochondrial electron transport chain (ETC) complexes I, II, III and V inhibitors all prevent NLRP3 inflammasome activation. Ectopic expression of Saccharomyces cerevisiae NADH dehydrogenase (NDI1) or Ciona intestinalis alternative oxidase (AOX), which can respectively complement the functional loss of mitochondrial complex I or III, without generation of ROS, rescued NLRP3 inflammasome activation in the absence of endogenous mitochondrial complex I or complex III function. Metabolomics revealed phosphocreatine (PCr), which can sustain ATP levels, as a common metabolite that is diminished by mitochondrial ETC inhibitors. PCr depletion decreased ATP levels and NLRP3 inflammasome activation. Thus, mitochondrial ETC sustains NLRP3 inflammasome activation through PCr-dependent generation of ATP but a ROS independent mechanism.
Project description:Controlling charge transport through molecules is challenging because it requires engineering of the energy of molecular orbitals involved in the transport process. While side groups are central to maintaining solubility in many molecular materials, their role in modulating charge transport through single-molecule junctions has received less attention. Here, using two break-junction techniques and computational modeling, we investigate systematically the effect of electron-donating and -withdrawing side groups on the charge transport through single molecules. By characterizing the conductance and thermopower, we demonstrate that side groups can be used to manipulate energy levels of the transport orbitals. Furthermore, we develop a novel statistical approach to model quantum transport through molecular junctions. The proposed method does not treat the electrodes' chemical potential as a free parameter and leads to more robust prediction of electrical conductance as confirmed by our experiment. The new method is generic and can be used to predict the conductance of molecules.
Project description:On-wire lithography (OWL) fabricated nanogaps are used as a new testbed to construct molecular transport junctions (MTJs) through the assembly of thiolated molecular wires across a nanogap formed between two Au electrodes. In addition, we show that one can use OWL to rapidly characterize a MTJ and optimize gap size for two molecular wires of different dimensions. Finally, we have used this new testbed to identify unusual temperature-dependent transport mechanisms for alpha,omega-dithiol terminated oligo(phenylene ethynylene).
Project description:Maquettes are man-made cofactor-binding oxidoreductases designed from first principles with minimal reference to natural protein sequences. Here we focus on water-soluble maquettes designed and engineered to perform diffusive electron transport of the kind typically carried out by cytochromes, ferredoxins and flavodoxins and other small proteins in photosynthetic and respiratory energy conversion and oxido-reductive metabolism. Our designs were tested by analysis of electron transfer between heme maquettes and the well-known natural electron transporter, cytochrome c. Electron-transfer kinetics were measured from seconds to milliseconds by stopped-flow, while sub-millisecond resolution was achieved through laser photolysis of the carbon monoxide maquette heme complex. These measurements demonstrate electron transfer from the maquette to cytochrome c, reproducing the timescales and charge complementarity modulation observed in natural systems. The ionic strength dependence of inter-protein electron transfer from 9.7×10(6) M(-1) s(-1) to 1.2×10(9) M(-1) s(-1) follows a simple Debye-Hückel model for attraction between +8 net charged oxidized cytochrome c and -19 net charged heme maquette, with no indication of significant protein dipole moment steering. Successfully recreating essential components of energy conversion and downstream metabolism in man-made proteins holds promise for in vivo clinical intervention and for the production of fuel or other industrial products. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson.
Project description:Molecular junctions formed using the scanning-tunneling-microscope-based break-junction technique (STM-BJ) have provided unique insight into charge transport at the nanoscale. In most prior work, the same metal, typically Au, Pt, or Ag, is used for both tip and substrate. For such noble metal electrodes, the density of electronic states is approximately constant within a narrow energy window relevant to charge transport. Here, we form molecular junctions using the STM-BJ technique, with an Au metal tip and a microfabricated graphite substrate, and measure the conductance of a series of graphite/amine-terminated oligophenyl/Au molecular junctions. The remarkable mechanical strength of graphite and the single-crystal properties of our substrates allow measurements over few thousand junctions without any change in the surface properties. We show that conductance decays exponentially with molecular backbone length with a decay constant that is essentially the same as that for measurements with two Au electrodes. More importantly, despite the inherent symmetry of the oligophenylamines, we observe rectification in these junctions. State-of-art ab initio conductance calculations are in good agreement with experiment, and explain the rectification. We show that the highly energy-dependent graphite density of states contributes variations in transmission that, when coupled with an asymmetric voltage drop across the junction, leads to the observed rectification. Together, our measurements and calculations show how functionality may emerge from hybrid molecular-scale devices purposefully designed with different electrodes beyond the so-called "wide band limit," opening up the possibility of assembling molecular junctions with dissimilar electrodes using layered 2D materials.