Junctional Conductance Research Articles

Why strengthening gap junctions may hinder action potential propagation

Gap junctions are channels in cell membranes allowing ions to pass directly between cells. They are found throughout the body, including heart myocytes, neurons, and astrocytes. In cardiac tissue and throughout the nervous system, an action potential (AP) in one cell can trigger APs in neighboring cells connected by gap junctions. It is known experimentally that there is an ideal gap junction conductance for AP propagation—lower or higher conductance can lead to propagation failure. We explain this phenomenon geometrically in branching networks by analyzing an idealized model that focuses exclusively on gap junction and AP-generating currents. As expected, the gap junction conductance must be high enough for AP propagation to occur. However, if the gap junction conductance is too high, then it dominates the cell's intrinsic firing conductance and disrupts AP generation. We also identify conditions for semi-active propagation, where cells in the network are not individually excitable but still propagate action potentials.

Solvent-Mediated Modulation of the Au-S Bond in Dithiol Molecular Junctions.

Gold-dithiol molecular junctions have been studied both experimentally and theoretically. However, the nature of the gold-thiolate bond as it relates to the solvent has seldom been investigated. It is known that solvents can impact the electronic structure of single-molecule junctions, but the correlation between the solvent and dithiol-linked single-molecule junction conductance is not well understood. We study molecular junctions formed with thiol-terminated phenylenes from both 1-chloronaphthalene and 1-bromonaphthalene solutions. We find that the most probable conductance and the distribution of conductances are both affected by the solvent. First-principles calculations show that junction conductance depends on the binding configurations (adatom, atop, and bridge) of the thiolate on the Au surface, as has been shown previously. More importantly, we find that brominated solvents can restrict the binding of thiols to specific Au sites. This mechanism offers new insight into the effects of the solvent environment on covalent bonding in molecular junctions.

Nernst-Planck-Gaussian modelling of electrodiffusional recovery from ephaptic excitation between mammalian cardiomyocytes.

Introduction: In addition to gap junction conduction, recent reports implicate possible ephaptic coupling contributions to action potential (AP) propagation between successive adjacent cardiomyocytes. Here, AP generation in an active cell, withdraws Na+ from, creating a negative potential within, ephaptic spaces between the participating membranes, activating the initially quiescent neighbouring cardiomyocyte. However, sustainable ephaptic transmission requires subsequent complete recovery of the ephaptic charge difference. We explore physical contributions of passive electrodiffusive ion exchange with the remaining extracellular space to this recovery for the first time. Materials and Methods: Computational, finite element, analysis examined limiting, temporal and spatial, ephaptic [Na+], [Cl-], and the consequent Gaussian charge differences and membrane potential recovery patterns following a ΔV∼130mV AP upstroke at physiological (37°C) temperatures. This incorporated Nernst-Planck formalisms into equations for the time-dependent spatial concentration gradient profiles. Results: Mammalian atrial, ventricular and purkinje cardiomyocyte ephaptic junctions were modelled by closely apposed circularly symmetric membranes, specific capacitance 1μF cm-2, experimentally reported radii a = 8,000, 12,000 and 40,000nm respectively and ephaptic axial distance w = 20nm. This enclosed an ephaptic space containing principal ions initially at normal extracellular [Na+] = 153.1mM and [Cl-] = 145.8 mM, respective diffusion coefficients D Na = 1.3 109 and D Cl = 2 109 nm2s-1. Stable, concordant computational solutions were confirmed exploring ≤1,600nm mesh sizes and Δt≤0.08ms stepsize intervals. The corresponding membrane voltage profile changes across the initially quiescent membrane were obtainable from computed, graphically represented a and w-dependent ionic concentration differences adapting Gauss's flux theorem. Further simulations explored biological variations in ephaptic dimensions, membrane anatomy, and diffusion restrictions within the ephaptic space. Atrial, ventricular and Purkinje cardiomyocytes gave 40, 180 and 2000ms 99.9% recovery times, with 720 or 360ms high limits from doubling ventricular radius or halving diffusion coefficient. Varying a, and D Na and D Cl markedly affected recovery time-courses with logarithmic and double-logarithmic relationships, Varying w exerted minimal effects. Conclusion: We thereby characterise the properties of, and through comparing atrial, ventricular and purkinje recovery times with interspecies in vivo background cardiac cycle duration data, (blue whale ∼2000, human∼90, Etruscan shrew, ∼40ms) can determine physical limits to, electrodiffusive contributions to ephaptic recovery.

Benchmarking break-junction techniques: electric and thermoelectric characterization of naphthalenophanes.

Break-junction techniques provide the possibility to study electric and thermoelectric properties of single-molecule junctions in great detail. These techniques rely on the same principle of controllably breaking metallic contacts in order to create single-molecule junctions, whilst keeping track of the junction's conductance. Here, we compare results from mechanically controllable break junction (MCBJ) and scanning tunneling microscope (STM) methods, while characterizing conductance properties of the same novel mechanosensitive para- and meta-connected naphtalenophane compounds. In addition, thermopower measurements are carried out for both compounds using the STM break junction (STM-BJ) technique. For the conductance experiments, the same data processing using a clustering analysis is performed. We obtain to a large extent similar results for both methods, although values of conductance and stretching lengths for the STM-BJ technique are slightly larger in comparison with the MCBJ. STM-BJ thermopower experiments show similar Seebeck coefficients for both compounds. An increase in the Seebeck coefficient is revealed, whilst the conductance decreases, after which it saturates at around 10 μV K-1. This phenomenon is studied theoretically using a tight binding model. It shows that changes of molecule-electrode electronic couplings combined with shifts of the resonance energies explain the correlated behavior of conductance and Seebeck coefficient.

Large area arrays of discrete single-molecule junctions derived from host-guest complexes.

The desire to continually reduce the lower limits of semiconductor integrated circuit (IC) fabrication methods continues to inspire interest in unimolecular electronics as a platform technology for the realization of future (opto)electronic devices. However, despite successes in developing methods for the construction and measurement of single-molecule and large-area molecular junctions, exercising control over the precise junction geometry remains a significant challenge. Here, host-guest complexes of the wire-like viologen derivative 1,1'-bis(4-(methylthio)-phenyl)-[4,4'-bipyridine]-1,1'-diium chloride ([1][Cl]2) and cucurbit[7]uril (CB[7]) have been self-assembled in a regular pattern over a gold substrate. Subsequently, ligandless gold nanoparticles (AuNPs) synthesized in situ are deposited over the host-guest array. The agreement between the conductance of individual mono-molecular junctions, appropriately chosen as a function of the AuNP diameter, within this array determined by conductive probe atomic force microscope (c-AFM) and true single-molecule measurements for a closely similar host-guest complex within a scanning tunneling microscope break-junction (STM-BJ) indicates the formation of molecular junctions derived from these host-guest complexes without deleterious intermolecular coupling effects.

Conductance and assembly of quasi-1D coordination chain molecular junctions with triazole derivatives.

Incorporating transition metal atoms into metal-molecule-metal junctions presents opportunities for exploring the electronic properties of coordination complexes, organometallics and metal-organic materials on the single molecule level. Recent single molecule conductance studies have shown that in situ incorporation of electrode metal atoms into coordination chains formed in the junction can occur with deprotonated, negatively charged organic ligands, such as the imidazolate (Im-) anion. However, the mechanism and chemical principles, such as the role of the charge state of the ligand, for the construction of such coordination chains are still debated. Here, we probe the role of the ligand charge state and electronic structure in single-molecule conductance and formation of metal-molecule coordination chains. We perform break junction measurements with triazole isomers, which can bridge junctions both in their neutral and charged forms, and find that prior deprotonation of the ligands is not required for coordination complex assembly, but can affect the molecular conductance and junction formation probability. Our results indicate that coordination chains can form with neutral ligands, as long as the electron density in the frontier MOs is concentrated at the binding sites and along the direction of pulling, promoting ligand binding and incorporation of gold atoms into the junction during elongation. Our findings may provide insight into design principles for in situ assembled molecular wires with transition metal atoms and open the door to electronic and spintronic studies of such materials.

The regulation effect of coordination number on the conductance of single-molecule junctions

The molecules with multiple anchoring sites offer opportunities for conductance regulation of single-molecule junctions via a switch between different coordination numbers.

Nanoarchitectonics of molecular self assembled monolayers by transition metal ion intercalation for enhancement of molecular junction conductivity.

This research delves into the role of metal ions in enhancing the electronic properties of 5,5'-bis(mercaptomethyl)-2,2'-bipyridine (BPD) self-assembled monolayers (SAMs). It combines experimental techniques and numerical simulations to understand the impact of these ions on the structural, electronic, and transport properties of BPD SAMs. Key findings include the varied bonding preferences of metal ions and their significant role in modifying the electronic structure of BPD molecules, leading to enhanced electron delocalization and migration. The study highlights the potential of metal ions in advancing molecular electronics, particularly in the development of high-performance electronic and energy devices.

Methods for the analysis, interpretation, and prediction of single-molecule junction conductance behaviour

This article provides an overview of measurement methods and interpretations of data in the field of molecular electronics, together with a summary of predictive models that assist in establishing robust structure–property relationships.

Electrical Conductance and Thermopower of β-Substituted Porphyrin Molecular Junctions─Synthesis and Transport.

Molecular junctions offer significant potential for enhancing thermoelectric power generation. Quantum interference effects and associated sharp features in electron transmission are expected to enable the tuning and enhancement of thermoelectric properties in molecular junctions. To systematically explore the effect of quantum interferences, we designed and synthesized two new classes of porphyrins, P1 and P2, with two methylthio anchoring groups in the 2,13- and 2,12-positions, respectively, and their Zn complexes, Zn-P1 and Zn-P2. Past theory suggests that P1 and Zn-P1 feature destructive quantum interference in single-molecule junctions with gold electrodes and may thus show high thermopower, while P2 and Zn-P2 do not. Our detailed experimental single-molecule break-junction studies of conductance and thermopower, the latter being the first ever performed on porphyrin molecular junctions, revealed that the electrical conductance of the P1 and Zn-P1 junctions is relatively close, and the same holds for P2 and Zn-P2, while there is a 6 times reduction in the electrical conductance between P1 and P2 type junctions. Further, we observed that the thermopower of P1 junctions is slightly larger than for P2 junctions, while Zn-P1 junctions show the largest thermopower and Zn-P2 junctions show the lowest. We relate the experimental results to quantum transport theory using first-principles approaches. While the conductance of P1 and Zn-P1 junctions is robustly predicted to be larger than those of P2 and Zn-P2, computed thermopowers depend sensitively on the level of theory and the single-molecule junction geometry. However, the predicted large difference in conductance and thermopower values between Zn-P1 and Zn-P2 derivatives, suggested in previous model calculations, is not supported by our experimental and theoretical findings.

Quantum bath augmented stochastic nonequilibrium atomistic simulations for molecular heat conduction.

Classical molecular dynamics (MD) has been shown to be effective in simulating heat conduction in certain molecular junctions since it inherently takes into account some essential methodological components which are lacking in the quantum Landauer-type transport model, such as many-body full force-field interactions, anharmonicity effects and nonlinear responses for large temperature biases. However, the classical MD reaches its limit in the environments where the quantum effects are significant (e.g. with low-temperatures substrates, presence of extremely high frequency molecular modes). Here, we present an atomistic simulation methodology for molecular heat conduction that incorporates the quantum Bose-Einstein statistics into an "effective temperature" in the form of a modified Langevin equation. We show that the results from such a quasi-classical effective temperature MD method deviates drastically when the baths temperature approaches zero from classical MD simulations and the results converge to the classical ones when the bath approaches the high-temperature limit, which makes the method suitable for full temperature range. In addition, we show that our quasi-classical thermal transport method can be used to model the conducting substrate layout and molecular composition (e.g. anharmonicities, high-frequency modes). Anharmonic models are explicitly simulated via the Morse potential and compared to pure harmonic interactions to show the effects of anharmonicities under quantum colored bath setups. Finally, the chain length dependence of heat conduction is examined for one-dimensional polymer chains placed in between quantum augmented baths.

Single-Molecule Conductance of Intramolecular Hydrogen Bonding in Histamine on Gold.

We perform single-molecule conductance measurements and DFT calculations on histamine, a biogenic amine that contains a flexible aliphatic linker and several nitrogen moieties with a potential for hydrogen bonding. Our study determines that junctions containing the free-base form of histamine can bridge through a molecular structure containing an intramolecular hydrogen bond. Conductance of this structure is higher than that through the saturated aliphatic linker. Flicker noise analysis of junction conductance confirms that transport occurs through the hydrogen bond and establishes a benchmark for noise measurements in hydrogen-bonded junctions. Overall, our work provides insights into the formation and conduction of intramolecular hydrogen bonding in single-molecule conductance measurements and into the conformations of the neurotransmitter histamine on noble metal surfaces.

The role of the Cx43/Cx45 gap junction voltage gating on wave propagation and arrhythmogenic activity in cardiac tissue

Gap junctions (GJs) formed of connexin (Cx) protein are the main conduits of electrical signals in the heart. Studies indicate that the transitional zone of the atrioventricular (AV) node contains heterotypic Cx43/Cx45 GJ channels which are highly sensitive to transjunctional voltage (Vj). To investigate the putative role of Vj gating of Cx43/Cx45 channels, we performed electrophysiological recordings in cell cultures and developed a novel mathematical/computational model which, for the first time, combines GJ channel Vj gating with a model of membrane excitability to simulate a spread of electrical pulses in 2D. Our simulation and electrophysiological data show that Vj transients during the spread of cardiac excitation can significantly affect the junctional conductance (gj) of Cx43/Cx45 GJs in a direction- and frequency-dependent manner. Subsequent simulation data indicate that such pulse-rate-dependent regulation of gj may have a physiological role in delaying impulse propagation through the AV node. We have also considered the putative role of the Cx43/Cx45 channel gating during pathological impulse propagation. Our simulation data show that Vj gating-induced changes in gj can cause the drift and subsequent termination of spiral waves of excitation. As a result, the development of fibrillation-like processes was significantly reduced in 2D clusters, which contained Vj-sensitive Cx43/Cx45 channels.

Conductance of Metallic Carbon Nanotubes Network

The conductance of the carbon nanotubes (CNTs) network incorporates intertube and intratube conductance. Using the Anderson and tight-binding models, we calculate both conductances in the armchair and chiral metallic CNTs. We found that, at room temperature, the intertube conductance dominates in CNTs with larger localization lengths. Intertube conductance includes electronic and phonon-assisted junction conductance. We have revealed that the electronic conductance of a relaxed structure is around an order of magnitude larger than an unrelaxed structure. We found that the phonon-assisted conductance of armchair CNTs is comparable with their electronic conductance. However, the phonon-assisted conductance of chiral CNTs is around seven times smaller than the electronic conductance due to the large momentum needed for momentum relaxation. Furthermore, we address the dependence of junction conductance on the angle between the CNTs, the twist angle and sliding shift of the CNTs, the Fermi energy, and the applied bias voltage between CNTs. Our calculations perfectly match the experimentally measured temperature-dependent conductance using a single geometrical fitting parameter.

Manipulating Quantum Interference between σ and π Orbitals in Single-Molecule Junctions via Chemical Substitution and Environmental Control.

Understanding and manipulating quantum interference (QI) effects in single molecule junction conductance can enable the design of molecular-scale devices. Here we demonstrate QI between σ and π molecular orbitals in an ∼4 Å molecule, pyrazine, bridging source and drain electrodes. Using single molecule conductance measurements, first-principles analysis, and electronic transport calculations, we show that this phenomenon leads to distinct patterns of electron transport in nanoscale junctions, such as destructive interference through the para position of a six-membered ring. These QI effects can be tuned to allow conductance switching using environmental pH control. Our work lays out a conceptual framework for engineering QI features in short molecular systems through synthetic and external manipulation that tunes the energies and symmetries of the σ and π channels.

Supramolecular Radical Electronics.

Supramolecular radical chemistry is an emerging area bridging supramolecular chemistry and radical chemistry, and the integration of radicals into the supramolecular architecture offers a new dimension for tuning their structures and functions. Although various efforts have been devoted to the fabrication of supramolecular junctions, the charge transport characterization through the supramolecular radicals remained unexplored due to the challenges in creating supramolecular radicals at the single-molecule level. Here, we demonstrate the fabrication and charge transport investigation of a supramolecular radical junction using the electrochemical scanning tunneling microscope-based break junction (EC-STM-BJ) technique. We found that the conductance of a supramolecular radical junction was more than 1 order of magnitude higher than that of a supramolecular junction without a radical and even higher than that of a fully conjugated oligophenylenediamine molecule with a similar length. The combined experimental and theoretical investigations revealed that the radical increased the binding energy and decreased the energy gap in the supramolecular radical junction, which leads to the near-resonant transport through the supramolecular radical. Our work demonstrated that the supramolecular radical can provide not only strong binding but also efficient electrical coupling between building blocks, which provides new insights into supramolecular radical chemistry and new materials with supramolecular radicals.

Cooperative Self-Assembly of Dimer Junctions Driven by π Stacking Leads to Conductance Enhancement.

We demonstrate enhanced electronic transport through dimer molecular junctions, which self-assemble between two gold electrodes in π-π stabilized binding configurations. Single molecule junction conductance measurements show that benzimidazole molecules assemble into dimer junctions with a per-molecule conductance that is higher than that in monomer junctions. Density functional theory calculations reveal that parallel stacking of two benzimidazoles between electrodes is the most energetically favorable due to the large π system. Imidazole is smaller and has greater conformational freedom to access different stacking angles. Transport calculations confirm that the conductance enhancement of benzimidazole dimers results from the changed binding geometry of dimers on gold, which is stabilized and made energetically accessible by intermolecular π stacking. We engineer imidazole derivatives with higher monomer conductance than benzimidazole and large intermolecular interaction that promote cooperative in situ assembly of more transparent dimer junctions and suggest at the potential of molecular devices based on self-assembled molecular layers.

Single-Atom Control of Single-Molecule van der Waals Junctions with Semimetallic Transition Metal Dichalcogenide Electrodes.

Electrodes play an essential role in controlling electrode-molecule coupling. However, conventional metal electrodes require linkers to anchor the molecule. Van der Waals interaction offers a versatile strategy to connect the electrode and molecule without anchor groups. Except for graphene, the potential of other materials as electrodes to fabricate van der Waals molecular junctions remains unexplored. Herein, we utilize semimetallic transition metal dichalcogenides (TMDCs) 1T'-WTe2 as electrodes to fabricate WTe2/metalated tetraphenylporphyrin (M-TPP)/WTe2 junctions via van der Waals interaction. Compared with chemically bonded Au/M-TPP/Au junctions, the conductance of these M-TPP van der Waals molecular junctions is enhanced by ∼736%. More importantly, WTe2/M-TPP/WTe2 junctions exhibit the tunable conductance from 10-3.29 to 10-4.44 G0 (1.15 orders of magnitude) via single-atom control, recording the widest tunable range of conductance for M-TPP molecular junctions. Our work demonstrates the potential of two-dimensional TMDCs for constructing highly tunable and conductive molecular devices.

Andreev reflection between aluminum and graphene across van der Waals barriers

We present planar aluminum superconductor–graphene junctions whose hybrid interface is engineered for couplings ranging from tunneling to the strongly coupled regime by employing an atomically thin van der Waals tunneling barrier. Without the vdW barrier, we find Al makes strongly coupled contacts with the fully proximities graphene channel underneath. Using a large band gap hexagonal boron nitride (hBN) barrier, we find the junctions always remain in the weak coupling regime, exhibiting tunneling characteristics. Using monolayer semi-conducting transition metal dichalcogenides (TMDs) such as MoS2, we realize intermediate coupling with enhanced junction conductance due to the Andreev process. In this intermediate regime, we find that junction resistance changes in discrete steps when sweeping a perpendicular magnetic field. The period of the resistance steps in the magnetic field is inversely proportional to the junction area, suggesting the physical origin of our observations is due to magnetic-field-induced vortex formation in the planar junction.

Revisiting Andreev processes in superconductor-graphene-superconductor (SGS) Josephson junctions: comparison with experimental results

In view of the recent progress in experiments on charge transport through various Josephson junctions made out of graphene, we have made a careful comparison between the theory and some of the available experimental results. Within the framework of a transfer matrix approach, we have first analytically derived the spectrum of Andreev bound states (ABS) in a superconductor -graphene-superconductor (SGS) junction for a wide range of experimentally relevant parameters. We have particularly considered the case of monolayer graphene (MLG). The theoretical results can account for both the retro Andreev reflection (RAR) and the specular Andreev reflection (SAR) in the relevant parameter range. Using the ABS spectrum we have evaluated the current through such junctions and the junction conductance from the analytically derived expressions at different bias voltages for a range of other system parameters directly taken from the experimental works. These theoretical results have then been compared with experimental results. Evaluated current and the conductance show scaling behaviour with change in the junction length and agree well with the experimental results. In the relevant parameter regime where the SAR process is dominant, the calculated values of the current and the conductivity have been found much lower than the corresponding values observed when the RAR process is dominant.