Explore the vast range of titles available.

Photolyase uses blue light to restore the major ultraviolet (UV)-induced DNA damage, the cyclobutane pyrimidine dimer (CPD), to two normal bases by splitting the cyclobutane ring. Our earlier studies showed that the overall repair is completed in 700 ps through a cyclic electron-transfer radical mechanism. However, the two fundamental processes, electron-tunneling pathways and cyclobutane ring splitting, were not resolved. Here, we use ultrafast UV absorption spectroscopy to show that the CPD splits in two sequential steps within 90 ps and the electron tunnels between the cofactor and substrate through a remarkable route with an intervening adenine. Site-directed mutagenesis reveals that the active-site residues are critical to achieving high repair efficiency, a unique electrostatic environment to optimize the redox potentials and local flexibility, and thus balance all catalytic reactions to maximize enzyme activity. These key findings reveal the complete spatio-temporal molecular picture of CPD repair by photolyase and elucidate the underlying molecular mechanism of the enzyme’s high repair efficiency.

The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently, microorganisms have adapted multiheme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Å. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level, how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces efficiently, remains a mystery thus far inaccessible to experiment. To shed light on this critical topic, we carried out extensive quantum mechanics/molecular mechanics simulations to calculate stepwise heme-to-heme electron transfer rates in the recently crystallized outer membrane deca-heme cytochrome MtrF. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 10 ⁴–10 ⁵ s ⁻¹, consistent with recently measured rates for the related multiheme protein complex MtrCAB. Intriguingly, our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: thermodynamically uphill steps occur only between electronically well-connected stacked heme pairs. This observation suggests that the protein evolved to harbor low-potential hemes without slowing down electron flow. These findings are particularly profound in light of the apparently well-conserved staggered cross-heme wire structural motif in functionally related outer membrane proteins.

Silicon (Si) nano-electronics is advancing towards the end of the Moore’s Law, as gate lengths of just a few nanometers have been already reported in state-of-the-art transistors. In the nanostructures that act as channels in transistors or depletion layers in pn diodes, the role of dopants becomes critical, since the transport properties depend on a small number of dopants and/or on their random distribution. Here, we present the possibility of single-charge tunneling in codoped Si nanodevices formed in silicon-on-insulator films, in which both phosphorus (P) donors and boron (B) acceptors are introduced intentionally. For highly doped pn diodes, we report band-to-band tunneling (BTBT) via energy states in the depletion layer. These energy states can be ascribed to quantum dots (QDs) formed by the random distribution of donors and acceptors in such a depletion layer. For nanoscale silicon-on-insulator field-effect transistors (SOI-FETs) doped heavily with P-donors and also counter-doped with B-acceptors, we report current peaks and Coulomb diamonds. These features are ascribed to single-electron tunneling (SET) via QDs in the codoped nanoscale channels. These reports provide new insights for utilizing codoped silicon nanostructures for fundamental applications, in which the interplay between donors and acceptors can enhance the functionalities of the devices.

Inelastic electron tunneling spectroscopy (IETS) has emerged as a powerful vibrational spectroscopy technique for molecular electronic junctions, providing unique insights into molecular vibrations and electron–phonon coupling at the nanoscale. In this review, we present a comprehensive overview of IETS in molecular junctions, tracing its development from foundational principles to the latest advances. We begin with the theoretical background, detailing the mechanisms by which inelastic tunneling processes generate vibrational fingerprints of molecules, and highlighting how IETS complements optical spectroscopies by accessing electrically driven vibrational excitations. We then discuss recent progress in experimental techniques and device architectures that have broadened the applicability of IETS. Central focus is given to emerging applications of IETS over the last decade: molecular sensing (identification of chemical bonds and conformational changes in junctions), thermoelectric energy conversion (probing vibrational contributions to molecular thermopower), molecular switches and functional devices (monitoring bias-driven molecular state changes via vibrational signatures), spintronic molecular junctions (detecting spin excitations and spin–vibration interplay), and advanced data analysis approaches such as machine learning for interpreting complex tunneling spectra. Finally, we discuss current challenges, including sensitivity at room temperature, spectral interpretation, and integration into practical devices. This review aims to serve as a thorough reference for researchers in physics, chemistry, and materials science, consolidating state-of-the-art understanding of IETS in molecular junctions and its growing role in molecular-scale device characterization.

We present a comprehensive vibrational spectroscopic analysis of vertical molecular junction devices constructed using single-layer graphene electrodes separated by an aryl alkane monolayer. In this work, inelastic electron tunneling spectroscopy (IETS) is employed to probe molecular vibrations within the junction, providing an in situ fingerprint of the molecules. Graphene has emerged as a promising electrode material for molecular electronics due to its atomically thin, mechanically robust nature and ability to form stable contacts. However, prior to this study, the vibrational spectra of molecules in graphene-based molecular junctions had not been fully explored. Here, we demonstrate that vertically stacked graphene electrodes can be used to form stable and reproducible molecular junctions that yield well-resolved IETS signatures. The observed IETS spectra exhibit distinct peaks corresponding to the vibrational modes of the sandwiched aryl alkane molecules, and all major features are assigned through density functional theory calculations of molecular vibrational modes. Furthermore, by analyzing the broadening of IETS peaks with temperature and AC modulation amplitude, we extract intrinsic vibrational linewidths, confirming that the spectral features originate from the molecular junction itself rather than extrinsic noise or instrumental artifacts. These findings conclusively verify the presence of the molecular layer between graphene electrodes as the charge transport pathway and highlight the potential of graphene–molecule–graphene junctions for fundamental studies in molecular electronics.

A theory of a thermally induced single-electron 'shuttling' instability in a magnetic nano-mechanical device subject to an external magnetic field is presented in the Coulomb blockade regime of electron transport. The model magnetic shuttle device considered comprises a movable metallic grain suspended between two magnetic leads, which are kept at different temperatures and assumed to be fully spin-polarized with anti-parallel magnetizations. For a given temperature difference shuttling is found to occur for a region of external magnetic fields between a lower and an upper critical field strength, which separate the shuttling regime from normal small-amplitude 'vibronic' regimes. We find that (i) the upper critical magnetic field saturates to a constant value in the high temperature limit and that the shuttle instability domain expands with a decrease of the temperature; (ii) the lower critical magnetic field depends not only on the temperature-independent phenomenological friction coefficient used in the model but also on intrinsic friction (which vanishes in the high temperature limit) caused by magnetic exchange forces and electron tunneling between the quantum dot and the leads. The feasibility of using thermally driven magnetic shuttle systems to harvest thermal breakdown phenomena is discussed.

Conventional biosensor designs are often vulnerable to issues like random dopant fluctuations (RDFs) and high thermal budgets due to their design and the device they are based on. The main reason behind such issues is the complexity of maintaining uniform doping levels throughout the device structure. This manuscript investigates a biosensor structure utilizing a dual pocket junctionless SiGe-Heterostructured TFET design to overcome such shortcomings. The implementation of the doping charge plasma technique with the uniform doping of 1 × 10 15 cm - 3 along an integrated SiGe-Heterostructure layer has improved the tunneling process while also effectively eliminating issues like random dopant fluctuations (RDF). Again the overall performance also depends on the sensitivity of the sensor design. Increasing the trapping area for biomolecules at the same technological node by increasing the pocket length or by adding a pocket region leads to rapid changes in the sensor’s electric properties owing to shifting dielectric constants (k) and charge densities (in both positive and negative situations), improving in the overall detection process. The influence of these parameters on the device’s Drain current, Surface Potential, Electron Tunneling Rate (ETR), Subthreshold Swing (SS), and I on /I off ratio is also explored. The introduction of the added pocket region gives us scalability while also showing a higher sensitivity of 5.38 × 10 9 for a dielectric constant being 12 and neutrally charged while rising to nearly 1.43 × 10 10 if the molecules are positively charged. With the improvement in drain current sensitivity due to the additional pocket and junctionless design, this work will undoubtedly give researchers a roadmap for the future generation of highly sensitive biosensor alternatives.

Inelastic electron tunneling spectroscopy (IETS) based on scanning tunneling microscopy (STM) opens a new avenue for vibrational spectroscopy at single bond level. Since its birth, STM-IETS has been widely used for chemical identification and investigating the intra- and inter-molecular interactions as well as chemical reactions. In this review, we mainly focus on the new development and application of STM-IETS in the past decade. After introducing the basic theoretical background of IETS, we will discuss the recent advances of STM-IETS as vibrational spectroscopy and microspectroscopy, with emphasis on the ability of probing weak intermolecular interactions. The coupling of inelastic tunneling electrons to other elementary excitations, such as rotation, phonon, spin, plasmon, photon, etc., will be also briefly reviewed. In the end, we present a perspective for the future directions and challenges of STM-IETS. The goal of this review is to demonstrate the versatility of STM-IETS and inspire new applications in interdisciplinary fields.

The optical and electrical characteristics of electrically-driven nanogap antennas are extremely sensitive to the nanogap region where the fields are tightly confined and electrons and photons can interplay. Upon injecting electrons in the nanogap, a conductance channel opens between the metal surfaces modifying the plasmon charge distribution and therefore inducing an electrical tuning of the gap plasmon resonance. Electron tunneling across the nanogap can be harnessed to induce broadband photon emission with boosted quantum efficiency. Under certain conditions, the energy of the emitted photons exceeds the energy of electrons, and this overbias light emission is due to spontaneous emission of the hot electron distribution in the electrode. We conclude with the potential of electrically controlled nanogap antennas for faster on-chip communication.

Expectation of fundamentally new phenomena owing to multiband superconductivity stimulates a search for novel materials with, at least, two distinct gaps in the superconducting state. Recent temperature-dependent electronic heat capacity and lower critical field measurements for molybdenum-rhenium alloys have revealed signatures of two-gap superconductivity. In this letter, we report a direct evidence of two superconducting energy gaps in a Mo1-xRex alloy films probed by single-electron tunneling spectroscopy. Earlier, it was found that the superconducting transition temperature Tc in the alloys with very close atomic concentrations of Mo and Re is about an order of magnitude higher than Tc’s of the constituent elements. Our observation of two distinct gaps in this system testifies in favor of the scenario that relates this enhancement to the interband interaction rather than to specific modifications of the molybdenium phonon spectrum after alloying with rhenium, i.e., a heavy mass defect.