Learning the relationship between nanoscale chemical patterning and hydrophobicity.

The hydrophobicity of proteins and similar surfaces, which display chemical heterogeneity at the nanoscale, drives countless aqueous interactions and assemblies. However, predicting how surface chemical patterning influences hydrophobicity remains a challenge. Here, we address this challenge by using molecular simulations and machine learning to characterize and model the hydrophobicity of a diverse library of patterned surfaces, spanning a wide range of sizes, shapes, and chemical compositions. We find that simple models, based only on polar content, are inaccurate, whereas complex neural network models are accurate but challenging to interpret. However, by systematically incorporating chemical correlations between surface groups into our models, we are able to construct a series of minimal models of hydrophobicity, which are both accurate and interpretable. Our models highlight that the number of proximal polar groups is a key determinant of hydrophobicity and that polar neighbors enhance hydrophobicity. Although our minimal models are trained on particular patch size and shape, their interpretability enables us to generalize them to rectangular patches of all shapes and sizes. We also demonstrate how our models can be used to predict hot-spot locations with the largest marginal contributions to hydrophobicity and to design chemical patterns that have a fixed polar content but vary widely in their hydrophobicity. Our data-driven models and the principles they furnish for modulating hydrophobicity could facilitate the design of novel materials and engineered proteins with stronger interactions or enhanced solubilities.

Surface NMR using quantum sensors in diamond.

NMR is a noninvasive, molecular-level spectroscopic technique widely used for chemical characterization. However, it lacks the sensitivity to probe the small number of spins at surfaces and interfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. To demonstrate the method's capabilities, aluminum oxide layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers. The surface NV-NMR technique detects spatially resolved NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real time the formation kinetics at the solid-liquid interface. With our approach, we show that NV quantum sensors are a surface-sensitive NMR tool with femtomole sensitivity for in situ analysis in catalysis, materials, and biological research.

Highly Reversible Molecular Photoswitches with Transition Metal Dichalcogenides Electrodes.

The molecule-electrode coupling plays an essential role in photoresponsive devices with photochromic molecules, and the strong coupling between the molecule and the conventional electrodes leads to/ the quenching effect and limits the reversibility of molecular photoswitches. In this work, we developed a strategy of using transition metal dichalcogenides (TMDCs) electrodes to fabricate the thiol azobenzene (TAB) self-assembled monolayers (SAMs) junctions with the eutectic gallium-indium (EGaIn) technique. The current-voltage characteristics of the EGaIn/GaOx //TAB/TMDCs photoswitches showed an almost 100% reversible photoswitching behavior, which increased by ∼28% compared to EGaIn/GaOx //TAB/AuTS photoswitches. Density functional theory (DFT) calculations showed the coupling strength of the TAB-TMDCs electrode decreased by 42% compared to that of the TAB-AuTS electrode, giving rise to improved reversibility. our work demonstrated the feasibility of 2D TMDCs for fabricating SAMs-based photoswitches with unprecedentedly high reversibility.

Magnetic Removal of Micro- and Nanoplastics from Water-from 100 nm to 100 µm Debris Size.

Clean water is one of the most important resources of the planet but human-made contamination with diverse pollutants increases continuously. Microplastics (<5 mm diameter) which can have severe impacts on the environment, are present worldwide. Degradation processes lead to nanoplastics (<1 µm), which are potentially even more dangerous due to their increased bioavailability. State-of-the-art wastewater treatment plants show a deficit in effectively eliminating micro- and nanoplastics (MNP) from water, particularly in the case of nanoplastics. In this work, the magnetic removal of three different MNP types across three orders of magnitude in size (100 nm-100 µm) is investigated systematically. Superparamagnetic iron oxide nanoparticles (SPIONs) tend to attract oppositely charged MNPs and form aggregates that can be easily collected by a magnet. It shows that especially the smallest fractions (100-300 nm) can be separated in ordinary high numbers (1013  mg-1 SPION) while the highest mass is removed for MNP between 2.5 and 5 µm. The universal trend for all three types of MNP can be fitted with a derived model, which can make predictions for optimizing SPIONs for specific size ranges in the future.

Electronic Devices Based on Heterostructures of 2D Materials and Self-Assembled Monolayers.

2D materials (2DMs), known for their atomically ultrathin structure, exhibit remarkable electrical and optical properties. Similarly, molecular self-assembled monolayers (SAMs) with comparable atomic thickness show an abundance of designable structures and properties. The strategy of constructing electronic devices through unique heterostructures formed by van der Waals assembly between 2DMs and molecular SAMs not only enables device miniaturization, but also allows for convenient adjustment of their structures and functions. In this review, the fundamental structures and fabrication methods of three different types of electronic devices dominated by 2DM-SAM heterojunctions with varying architectures are timely elaborated. Based on these heterojunctions, their fundamental functionalities and characteristics, as well as the regulation of their performance by external stimuli, are further discussed.

LiF-Rich Solid Electrolyte Interphase Formation by Establishing Sacrificial Layer on the Separator.

The formation of a stable solid electrolyte interphase (SEI) layer is crucial for enhancing the safety and lifespan of Li metal batteries. Fundamentally, a homogeneous Li+ behavior by controlling the chemical reaction at the anode/electrolyte interface is the key to establishing a stable SEI layer. However, due to the highly reactive nature of Li metal anodes (LMAs), controlling the movement of Li+ at the anode/electrolyte interface remains challenging. Here, an advanced approach is proposed for coating a sacrificial layer called fluorinated self-assembled monolayer (FSL) on a boehmite-coated polyethylene (BPE) separator to form a stable SEI layer. By leveraging the strong affinity between the fluorine functional group and Li+, the rapid formation of a LiF-rich SEI layer in the cell production and early cycling stage is facilitated. This initial stable SEI formation promotes the subsequent homogeneous Li+ flux, thereby improving the LMA stability and yielding an enhanced battery lifespan. Further, the mechanism behind the stable SEI layer generation by controlling the Li+ dynamics through the FSL-treated BPE separator is comprehensively verified. Overall, this research offers significant contributions to the energy storage field by addressing challenges associated with LMAs, thus highlighting the importance of interfacial control in achieving a stable SEI layer.

Gold nanoparticle-powered screening of membrane protein-specific lipids from complex lipid mixtures.

Membrane proteins (MPs) are affected by binding of specific lipids. We previously developed a methodology for systematically analyzing MP-lipid interactions leveraging surface plasmon resonance (SPR). In this method, the gold sensor chip surface was modified with a self-assembled monolayer (SAM), which allowed for a larger amount of MP-immobilization. However, the laborious lipid purification step remained a bottleneck. To address this issue, a new strategy has been developed utilizing gold nanoparticles (AuNPs) instead of the gold sensor chip. AuNPs were coated with SAM, on which MP was covalently anchored. The MP-immobilized AuNPs were mixed with a lipid mixture, and the recovered lipids were quantified by LC-MS. Bacteriorhodopsin (bR) was used as an MP to demonstrate this concept. We optimized immobilization conditions and confirmed the efficient immobilization of bR by dynamic light scattering and electron micrographs. Washing conditions for pulldown experiments were optimized to efficiently remove non-specific lipids. A new binding index was introduced to qualitatively reproduce the known affinity of lipids for bR. Consequently, the low-abundant and least-studied lipid S-TeGD was identified as a candidate for bR-specific lipids. This technique can skip the laborious lipid purification process, accelerating the screening of MP-specific lipids from complex lipid mixtures.

Low-cost portable sensor for rapid and sensitive detection of Pb2+ ions using capacitance sensing integrated with microfluidic enrichment.

Lead ion (Pb2+) pollution is a critical global issue due to its ability to accumulate in the human body, resulting in severe health problems. Despite extensive research efforts devoted to the detection of Pb2+ contamination, practical, rapid, and field-deployable sensors for Pb2+ is yet to be developed to effectively safeguard the environment and public health. Herein, a label-free affinity-based sensing device is developed based on printed circuit board (PCB) for low-cost, easy-to-use, and real-time on-site detection of Pb2+ ions. The sensors are prepared by forming a self-assembled monolayer of glutathione (GSH) on the surface of gold-plated PCB electrodes, which serves as a molecular probe to recognize Pb2+. Rapid and sensitive detection is achieved by using capacitance sensing integrated with microfluidic enrichment. The sensor's interfacial capacitance is used to indicate specific binding, while the capacitance reading process simultaneously induces alternating current electrothermal (ACET) acceleration of analyte's travel towards the probes. Thus, the enrichment and detection are integrated into a single step, making pre-concentration unnecessary and shortening the assay time to 30 s. This Pb2+ sensor has demonstrated one of the lowest limits of detection reported so far (1.85 fM) with a linear range of 0.01-10 pM. To evaluate the sensor's specificity, non-target metal ions are tested, all showing negligible responses. Testing of tap water sample also yields reasonable results, validating the sensor's robustness. The above-mentioned features, together with a commercial portable readout, make this sensor well-suited for point-of-use Pb2+ detection at low cost.

Multiphysics Modeling of Electrochemical Impedance Spectroscopy Responses of SAM-Modified Screen-Printed Electrodes.

In this work, we present a multiphysics modeling approach capable of simulating electrochemical impedance spectroscopy (EIS) responses of screen-printed electrodes (SPEs) modified with self-assembled monolayers of 11-Mercaptoundecanoic acid (MUA). Commercially available gold SPEs are electrochemically characterized through experimental cyclic voltammetry and EIS measurements with 10 mM [Fe(CN)6]3-/4- redox couple in phosphate buffered saline before and after the surface immobilization of MUA at different concentrations. We design the multiphysics model through COMSOL Multiphysics® based on the 3D geometry of the devices under test. The model includes four different physics considering the metal/solution interface electrochemical phenomena, the ion and electron potentials and currents, and the measurement set-up. The model is calibrated through a set of experimental measurements, allowing the tuning of the parameters used by the model. We use the calibrated model to simulate the EIS response of MUA-modified SPEs, comparing the results with experimental data. The simulations fit the experimental curves well, following the variation of MUA concentration on the surface from 1 µM to 100 µM. The EIS parameters, retrieved through a CPE-modified Randles' circuit, confirm the consistency with the experimental data. Notably, the simulated surface coverage estimates and the variation of charge transfer resistance due to MUA-immobilization are well matched with their experimental counterparts, reporting only a 2% difference and being consistent with the experimental electrochemical behavior of the SPEs.

Negative Charge-Carrying Glycans Attached to Exosomes as Novel Liquid Biopsy Marker.

Prostate cancer (PCa) is the second most common cancer. In this paper, the isolation and properties of exosomes as potential novel liquid biopsy markers for early PCa liquid biopsy diagnosis are investigated using two prostate human cell lines, i.e., benign (control) cell line RWPE1 and carcinoma cell line 22Rv1. Exosomes produced by both cell lines are characterised by various methods including nanoparticle-tracking analysis, dynamic light scattering, scanning electron microscopy and atomic force microscopy. In addition, surface plasmon resonance (SPR) is used to study three different receptors on the exosomal surface (CD63, CD81 and prostate-specific membrane antigen-PMSA), implementing monoclonal antibodies and identifying the type of glycans present on the surface of exosomes using lectins (glycan-recognising proteins). Electrochemical analysis is used to understand the interfacial properties of exosomes. The results indicate that cancerous exosomes are smaller, are produced at higher concentrations, and exhibit more nega tive zeta potential than the control exosomes. The SPR experiments confirm that negatively charged α-2,3- and α-2,6-sialic acid-containing glycans are found in greater abundance on carcinoma exosomes, whereas bisecting and branched glycans are more abundant in the control exosomes. The SPR results also show that a sandwich antibody/exosomes/lectins configuration could be constructed for effective glycoprofiling of exosomes as a novel liquid biopsy marker.

Fully Aromatic Self-Assembled Hole-Selective Layer toward Efficient Inverted Wide-Bandgap Perovskite Solar Cells with Ultraviolet Resistance.

Ultraviolet-induced degradation has emerged as a critical stability concern impeding the widespread adoption of perovskite solar cells (PSCs), particularly in the context of phase-unstable wide-band gap perovskite films. This study introduces a novel approach by employing a fully aromatic carbazole-based self-assembled monolayer, denoted as (4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)phosphonic acid (MeO-PhPACz), as a hole-selective layer (HSL) in inverted wide-band gap PSCs. Incorporating a conjugated linker plays a pivotal role in promoting the formation of a dense and highly ordered HSL on substrates, facilitating subsequent perovskite interfacial interactions, and fostering the growth of uniform perovskite films. The high-quality film could effectively suppress interfacial non-radiative recombination, improving hole extraction/transport efficiency. Through these advancements, the optimized wide-band gap PSCs, featuring a band gap of 1.68 eV, attain an impressive power conversion efficiency (PCE) of 21.10 %. Remarkably, MeO-PhPACz demonstrates inherent UV resistance and heightened UV absorption capabilities, substantially improving UV resistance for the targeted PSCs. This characteristic holds significance for the feasibility of large-scale outdoor applications.

Regulating Electric Double Layer via Self-Assembled Monolayer for Stable Solid/Electrolyte Interphase on Mg Metal Anode.

Modulating the cationic solvation structure with high donor-number (DN) additive is an effective strategy to construct a stable solid electrolyte interphase (SEI) on the Mg anode, which necessitates meticulous consideration of electrolyte chemistry and substantial quantities of additives. Notably, the electric double layer (EDL) adjacent to anode is pivotal role in SEI formation yet remains understudied. In this study, we propose a novel self-assembled monolayer (SAM) strategy by utilizing (trifluoromethyl)trimethylsilane (TFTMS, only 2 vol%, 1.4 mol%, 0.135 mol L-1), a low DN but strong Mg metal absorbability through electron-withdrawing groups(-CF3), to modulate the complex structure of the Helmholtz absorption plane. Through dipole-dipole interaction between the electronegative fluorine (-CF3 of TFTMS) and electropositive hydrogen (-CH3/-CH2 of solvents), TFTMS weakens solvent-Mg2+ coordination and thus enhances anion-Mg2+ interaction, inducing a stable and dense SEI with superior electronic insulation to realize horizontal Mg plating/stripping. Consequently, the designed electrolytes enable the symmetric cells to cycle stable for up to 1000 hours and reversible Mg plating/stripping under 5 mA cm-2, they show favorable compatibility with various cathodes. More importantly, the SAM strategy has good generality in other electrolyte systems, demonstrating a simple and effective route to promote the practical application of rechargeable magnesium battery.

Blocking Interfacial Proton Transport via Self-Assembled Monolayer for Hydrogen Evolution-Free Zinc Batteries.

Aqueous Zn-ion batteries (ZIBs) are promising next-generation energy storage devices, yet suffer from the issues of hydrogen evolution reaction (HER) and intricate side reactions on the Zn anode surface. The hydrogen (H)-bond networks play a critical role in interfacial proton transport that may closely relate to HER but are rarely investigated. Herein, we report a self-assembled monolayer (SAM) strategy which is constructed by anchoring ionic liquid cations on Ti3C2Tx substrate for HER-free Zn anode. Molecule dynamics simulations reveal that the rationally designed SAM with a high coordination number of water molecules (25-27, 4-6 for Zn2+) largely reduces the interfacial densities of H2O molecules, therefore breaking the connectivity of H-bond networks and blocking proton transport on the interface, by which the HER is suppressed. Then, a series of in situ characterizations demonstrate that negligible amounts of H2 gas are collected from the Zn@SAM-MXene anode. Consequently, the symmetric cell enables a long-cycling life of 3000 h at 1 mA cm-2 and 1000 h at 5 mA cm-2. More significantly, the stable Zn@SAM-MXene films are successfully used for coin full cells showing high-capacity retention of over 94 % after 1000 cycles and large-area (10×5 cm2) pouch cells with desired performance.

Survey of oligoethylene glycol-based self-assembled monolayers on electrochemical aptamer-based sensor in biological fluids.

The ability to monitor levels of endogenous markers and clearance profiles of drugs and their metabolites can improve the quality of biomedical research and precision with which therapies are individualized. Towards this end, electrochemical aptamer-based (EAB) sensors have been developed that support the real-time monitoring of specific analytes in vivo with clinically relevant specificity and sensitivity. A challenge associated with the in vivo deployment of EAB sensors, however, is how to manage the signal drift which, although correctable, ultimately leads to unacceptably low signal-to-noise ratios, limiting the measurement duration. Motivated by the correction of signal drift, in this paper, we have explored the use of oligoethylene glycol (OEG), a widely employed antifouling coating, to reduce the signal drift in EAB sensors. Counter to expectations, however, when challenged in 37 °C whole blood in vitro, EAB sensors employing OEG-modified self-assembled monolayers exhibit both greater drift and reduced signal gain, compared with those employ a simple, hydroxyl-terminated monolayer. On the other hand, when EAB sensor was prepared with a mix monolayer using MCH and lipoamido OEG 2 alcohol, reduced signal noise was observed compared to the same sensor prepared with MCH presumably due to improved SAM construction. These results suggest broader exploration of antifouling materials will be required to improve the signal drift of EAB sensors.

Key research development by Prof Mark Reed in molecular electronic devices.

In memory of Professor Mark Reed, who passed away on May 5, 2021, this article summarizes a series of his past groundbreaking developments in molecular electronic devices. Specifically, three key reports are summarized; measurement of the electrical conductance of molecular junctions using the mechanically controlled break junction technique and demonstration of negative differential resistance and orbital gating effect observed in molecular junctions. Also, a brief outlook on molecular electronics research field is addressed.

Batteryless wireless magnetostrictive Fe30Co70/Ni clad plate for human coronavirus 229E detection.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has been garnered increasing for its rapid worldwide spread. Each country had implemented city-wide lockdowns and immigration regulations to prevent the spread of the infection, resulting in severe economic consequences. Materials and technologies that monitor environmental conditions and wirelessly communicate such information to people are thus gaining considerable attention as a countermeasure. This study investigated the dynamic characteristics of batteryless magnetostrictive alloys for energy harvesting to detect human coronavirus 229E (HCoV-229E). Light and thin magnetostrictive Fe-Co/Ni clad plate with rectification, direct current (DC) voltage storage capacitor, and wireless information transmission circuits were developed for this purpose. The power consumption was reduced by improving the energy storage circuit, and the magnetostrictive clad plate under bending vibration stored a DC voltage of 1.9 V and wirelessly transmitted a signal to a personal computer once every 5 min and 10 s under bias magnetic fields of 0 and 10 mT, respectively. Then, on the clad plate surface, a novel CD13 biorecognition layer was immobilized using a self-assembled monolayer of -COOH groups, thus forming an amide bond with -NH2 groups for the detection of HCoV-229E. A bending vibration test demonstrated the resonance frequency changes because of HCoV-229E binding. The fluorescence signal demonstrated that HCoV-229E could be successfully detected. Thus, because HCoV-229E changed the dynamic characteristics of this plate, the CD13-modified magnetostrictive clad plate could detect HCoV-229E from the interval of wireless communication time. Therefore, a monitoring system that transmits/detects the presence of human coronavirus without batteries will be realized soon.

Electrochemical nano-biosensor based on electrospun indium zinc oxide nanofibers for the determination of complement component 3 protein.

Age-related macular degeneration (AMD) is a progressive chronic neurodegenerative retinal disease leading to vision loss, irreversible blindness, and visual impairment in older adults worldwide. Complement component 3 (C3) protein has been identified as the most predominant biomarker towards early diagnosis of AMD; therefore, there is an utmost requirement for non-invasive detection of C3 protein in the tear fluids of AMD patients. Considering this, we report an insightful electrochemical sensor capable of detecting clinically relevant concentrations ranging from 10 fg/mL to 1 µg/mL using electrospun indium-doped zinc oxide (InZnO) nanofibers as the transducing layer. The InZnO nanofibers have facilitated high anti-C3 antibody loading of 3.42 × 10-9 mol/cm2 and enhanced the overall charge transport mechanism at the sensor interface. The biofunctionalization process of the biosensor was investigated thoroughly using X-ray photoelectron spectroscopy (XPS) as well as different electrochemical techniques. The target C3 proteins were captured on the fabricated biosensor surface and determined through changes in charge transfer resistance (RCT) while executing electrochemical impedance spectroscopy (EIS) and peak current (Ip) in the case of cyclic voltammetry (CV) and differential pulse voltammetry (DPV), respectively. The InZnO nanofiber-based nano-biosensor demonstrated a very low limit of detections (LODs) of 5.214 fg/mL and 0.241 fg/mL with an excellent sensitivity of 4.6709 (ΔR/R) (g/mL)-1 cm-2 and 54.4939 (ΔIp/Ip)% (g/mL)-1 cm-2 for EIS and DPV techniques, respectively. By virtue of high antibody loading, ultrasensitive and ultra-selective capability, the indium-doped ZnO nanofibers show huge potential to be used as a high-performance diagnostic platform for AMD diagnosis.

Thermopower of Molecular Junction in Harsh Thermal Environments.

Molecular junctions can be miniaturized devices for heat-to-electricity conversion application, yet these operate only in mild thermal environments (less than 323 K) because thiol, the most widely used anchor moiety for chemisorption of active molecules onto surface of electrode, easily undergoes thermal degradation. N-Heterocyclic carbene (NHC) can be an alternative to traditional thiol anchor for producing ultrastable thermoelectric molecular junctions. Our experiments showed that the NHC-based molecular junctions withstood remarkably high temperatures up to 573 K, exhibiting consistent Seebeck effect and thermovoltage up to approximately |1900 µV|. Our work advances our understanding of molecule-electrode contact in the Seebeck effect, providing a roadmap for constructing robust and efficient organic thermoelectric devices.

Detection of Aromatic Hydrocarbons in Aqueous Solutions Using Quartz Tuning Fork Sensors Modified with Calix[4]arene Methoxy Ester Self-Assembled Monolayers: Experimental and Density Functional Theory Study.

Quartz tuning forks (QTFs), which were coated with gold and with self-assembled monolayers (SAM) of a lower-rim functionalized calix[4]arene methoxy ester (CME), were used for the detection of benzene, toluene, and ethylbenzene in water samples. The QTF device was tested by measuring the respective frequency shifts obtained using small (100 µL) samples of aqueous benzene, toluene, and ethylbenzene at four different concentrations (10-12, 10-10, 10-8, and 10-6 M). The QTFs had lower limits of detection for all three aromatic hydrocarbons in the 10-14 M range, with the highest resonance frequency shifts (±5%) being shown for the corresponding 10-6 M solutions in the following order: benzene (199 Hz) > toluene (191 Hz) > ethylbenzene (149 Hz). The frequency shifts measured with the QTFs relative to that in deionized water were inversely proportional to the concentration/mass of the analytes. Insights into the effects of the alkyl groups of the aromatic hydrocarbons on the electronic interaction energies for their hypothetical 1:1 supramolecular host-guest binding with the CME sensing layer were obtained through density functional theory (DFT) calculations of the electronic interaction energies (ΔIEs) using B3LYP-D3/GenECP with a mixed basis set: LANL2DZ and 6-311++g(d,p), CAM-B3LYP/LANL2DZ, and PBE/LANL2DZ. The magnitudes of the ΔIEs were in the following order: [Au4-CME⊃[benzene] > [Au4-CME]⊃[toluene] > [Au4-CME]⊃[ethylbenzene]. The gas-phase BSSE-uncorrected ΔIE values for these complexes were higher, with values of -96.86, -87.80, and -79.33 kJ mol-1, respectively, and -86.39, -77.23, and -67.63 kJ mol-1, respectively, for the corresponding BSSE-corrected values using B3LYP-D3/GenECP with LANL2dZ and 6-311++g(d,p). The computational findings strongly support the experimental results, revealing the same trend in the ΔIEs for the proposed hypothetical binding modes between the tested analytes with the CME SAMs on the Au-QTF sensing surfaces.

Supramolecular Memristor Based on Bistable [2]Catenanes: Toward High-Density and Non-Volatile Memory Devices.

The ever-increasing demand for data storage and neuromorphic computing calls for innovative, high-density solutions, such as resistive random-access memory (RRAM). However, the integration of resistive switching and rectification at the nanoscale remains a formidable challenge. In this study, we introduce a bistable [2]catenane-based supramolecular junction that simultaneously functions as a resistive switch and a diode. All supramolecular junctions are highly stable and reproducible over thousands of resistive switching cycles, because the nano-confinement of two mechanically interlocked rings can stabilize the radical states of pyridinium moieties under ambient conditions. The successful realization of supramolecular junctions in functionality with a thickness of approximately 2 nm presents a promising avenue for the development of molecule-scale based RRAM for a better solution to high density and energy efficiency.