Molecular Devices Research Articles

NETosis-Inspired Cell Surface-Constrained Framework Nucleic Acids Traps (FNATs) for Cascaded Extracellular Recognition and Cellular Behavior Modulation.

Upon pathogenic stimulation, activated neutrophils release nuclear DNA into the extracellular environment, forming web-like DNA structures known as neutrophil extracellular traps (NETs), which capture and kill bacteria, fungi, and cancer cells. This phenomenon is commonly referred to as NETosis. Inspired by this, we introduce a cell surface-constrained web-like framework nucleic acids traps (FNATs) with programmable extracellular recognition capability and cellular behavior modulation. This approach facilitates dynamic key chemical signaling molecule recognition such as adenosine triphosphate (ATP), which is elevated in the extracellular microenvironment, and triggers FNA self-assembly. This, in turn, leads to in situ tightly interwoven FNAs formation on the cell surface, thereby inhibiting target cell migration. Furthermore, it activates a photosensitizer-capturing switch, chlorin e6 (Ce6), and induces cell self-destruction. This cascade platform provides new potential tools for visualizing dynamic extracellular activities and manipulating cellular behaviors using programmable in situ self-assembling DNA molecular devices.

NETosis‐Inspired Cell Surface‐Constrained Framework Nucleic Acids Traps (FNATs) for Cascaded Extracellular Recognition and Cellular Behavior Modulation

AbstractUpon pathogenic stimulation, activated neutrophils release nuclear DNA into the extracellular environment, forming web‐like DNA structures known as neutrophil extracellular traps (NETs), which capture and kill bacteria, fungi, and cancer cells. This phenomenon is commonly referred to as NETosis. Inspired by this, we introduce a cell surface‐constrained web‐like framework nucleic acids traps (FNATs) with programmable extracellular recognition capability and cellular behavior modulation. This approach facilitates dynamic key chemical signaling molecule recognition such as adenosine triphosphate (ATP), which is elevated in the extracellular microenvironment, and triggers FNA self‐assembly. This, in turn, leads to in situ tightly interwoven FNAs formation on the cell surface, thereby inhibiting target cell migration. Furthermore, it activates a photosensitizer‐capturing switch, chlorin e6 (Ce6), and induces cell self‐destruction. This cascade platform provides new potential tools for visualizing dynamic extracellular activities and manipulating cellular behaviors using programmable in situ self‐assembling DNA molecular devices.

Effect of Bridging Manner on the Transport Behaviors of Dimethyldihydropyrene/Cyclophanediene Molecular Devices.

A molecule-electrode interface with different coupling strengths is one of the greatest challenges in fabricating reliable molecular switches. In this paper, the effects of bridging manner on the transport behaviors of a dimethyldihydropyrene/cyclophanediene (DHP/CPD) molecule connected to two graphene nanoribbon (GNR) electrodes have been investigated by using the non-equilibrium Green's function combined with density functional theory. The results show that both current values and ON/OFF ratios can be modulated to more than three orders of magnitude by changing bridging manner. Bias-dependent transmission spectra and molecule-projected self-consistent Hamiltonians are used to illustrate the conductance and switching feature. Furthermore, we demonstrate that the bridging manner modulates the electron transport by changing the energy level alignment between the molecule and the GNR electrodes. This work highlights the ability to achieve distinct conductance and switching performance in single-molecular junctions by varying bridging manners between DHP/CPD molecules and GNR electrodes, thus offering practical insights for designing molecular switches.

Alternative CNDOL Fockians for fast and accurate description of molecular exciton properties.

CNDOL is an a priori, approximate Fockian for molecular wave functions. In this study, we employ several modes of singly excited configuration interaction (CIS) to model molecular excitation properties by using four combinations of the one electron operator terms. Those options are compared to the experimental and theoretical data for a carefully selected set of molecules. The resulting excitons are represented by CIS wave functions that encompass all valence electrons in the system for each excited state energy. The Coulomb-exchange term associated to the calculated excitation energies is rationalized to evaluate theoretical exciton binding energies. This property is shown to be useful for discriminating the charge donation ability of molecular and supermolecular systems. Multielectronic 3D maps of exciton formal charges are showcased, demonstrating the applicability of these approximate wave functions for modeling properties of large molecules and clusters at nanoscales. This modeling proves useful in designing molecular photovoltaic devices. Our methodology holds potential applications in systematic evaluations of such systems and the development of fundamental artificial intelligence databases for predicting related properties.

Implication of carbohydrazide chemosensors in selective sensing of Fe(III) and construction of molecular devices

Two new and two reference sensors L1-L2 and R1-R2, respectively, based on the hydrazide core were synthesized in good yields (70–86 %). A variety of analytical methods, including NMR, HRMS, and single-crystal XRD, were used to characterize these sensors. Cyclic voltammetry, UV–visible absorption, and emission spectroscopies were then used to confirm the electrochemical and photophysical characteristics of these sensors. Moreover, theoretical calculations at the level of DFT and TD-DFT were carried out to compare the experimental findings with the theoretical ones. The sensors were found to exhibit luminescence attributed to singlet ligand-centered (1LC) transitions. Based on their luminescent properties and the previous literature reports where structurally analogous sensors have been used for the detection of metal ions, these sensors were investigated as selective chemosensors for Fe(III) detection, with a "turn-off" fluorescence behaviour in a binding stoichiometry of 1:1 = sensor:M(III) [M = Fe(III)] with a limit of detection of 2.71–39 µM, or 0.15–2.81 ppm. The mechanistic details regarding the sensing of Fe(III) ion by the sensors was provided by NMR, IR, XPS and UV-visible absorption spectroscopic studies. To increase the usefulness of the sensors, L2 was also applied for the successful fabrication of the molecular logic gate and molecular lock keypad. Paper strip test and sensing of Fe(III) contaminated water by the sensors accounted for the practical applicability of the sensors in real life.

Molecular Point-of-Care Assay Development: Design and Considerations.

Molecular diagnostic point-of-care (MDx POC) testing is gaining momentum and is increasingly important for infectious disease detection and monitoring, as well as other diagnostic areas such as oncology. Molecular testing has traditionally required high-complexity laboratories. Laboratory testing complexity is determined by utilizing the Clinical Laboratory Improvement Amendments of 1988 (CLIA) Categorization Criteria scorecard, utilizing seven criteria that are scored on a scale of one to three. Previously, most commercially available point-of-care (POC) tests use other analytes and technologies that were not found to be highly complex by the CLIA scoring system. However, during the COVID-19 pandemic, MDx POC testing became much more prominent. Utilization during the COVID-19 pandemic has demonstrated that MDx POC testing applications can have outstanding advantages compared to available non-molecular POC diagnostic tests. This article introduces MDx POC testing to students, technologists, researchers, and others, providing a general algorithm for MDx POC test development. This algorithm is an introductory, step-by-step decision tree for defining a molecular POC diagnostic device meeting the functional requirements for a desired application. The technical considerations driving the decision-making include nucleic acid selection method (DNA, RNA), extraction methods, sample preparation, number of targets, amplification technology, and detection method. The scope of this article includes neither higher-order multiplexing, nor quantitative molecular analysis. This article covers key application considerations, such as sensitivity, specificity, turnaround time, and shipping/storage requirements. This article provides an overall understanding of the best resources and practices to use when developing a MDx POC assay that may be a helpful resource for readers without extensive molecular testing experience as well as for those who are already familiar with molecular testing who want to increase MDx availability at the POC. © 2024 Wiley Periodicals LLC.

Exploring non-steady-state charge transport dynamics in information processing: insights from reservoir computing

Exploring nonlinear chemical dynamic systems for information processing has emerged as a frontier in chemical and computational research, seeking to replicate the brain’s neuromorphic and dynamic functionalities. In this study, we have extensively explored the information processing capabilities of a nonlinear chemical dynamic system through theoretical simulation by integrating a non-steady-state proton-coupled charge transport system into reservoir computing (RC) architecture. Our system demonstrated remarkable success in tasks such as waveform recognition, voice identification and chaos system prediction. More importantly, through a quantitative study, we revealed that the alignment between the signal processing frequency of the RC and the characteristic time of the dynamics of the nonlinear system plays a crucial role in this physical reservoir’s performance, directly influencing the efficiency in the task execution, the reservoir states and the memory capacity. The processing frequency range was further modulated by the characteristic time of the dynamic system, resulting in an implementation akin to a ‘chemically-tuned band-pass filter’ for selective frequency processing. Our study thus elucidates the fundamental requirements and dynamic underpinnings of the non-steady-state charge transport dynamic system for RC, laying a foundational groundwork for the application of dynamical molecular scale devices for in-materia neuromorphic computing.

Controllable antiresonance and low-bias negative differential conductance in T-shaped double dots with electron–phonon interaction

Controlling the quantum interference in nanoscaled systems has potential application for the realization of high-performance functional devices. In this work, the quantum interference of a T-shaped double-quantum-dot system is studied in detail by evaluation of differential conductance by means of nonequilibrium Green’s function method. The factors of Coulomb interaction in Luttinger liquid leads, electron–phonon interaction, interdot tunneling, and dot-lead coupling are taken into account. In the differential conductance curve, there appear a series of antiresonance dips due to phonon-assisted destructive interference when the interdot tunneling is weak, and they can coexist with zero-bias antiresonance dip. When the dot-lead couplings are asymmetric, both the antiresonance dip and Fano line shape dip can occur for strong dot-lead coupling. Our results also show the coexistence of low-bias negative differential conductance and Fano antiresonance, as a manifestation of the interplay between strong intralead Coulomb interaction and weak dot-lead coupling. These interference phenomena emerged in a relatively simple model promises helpful guidance for controlling over the electrical performance of interference-based molecular devices.

Toward Practical Single-Molecule/Atom Switches.

Electronic switches have been considered to be one of the most important components of contemporary electronic circuits for processing and storing digital information. Fabricating functional devices with building blocks of atomic/molecular switches can greatly promote the minimization of the devices and meet the requirement of high integration. This review highlights key developments in the fabrication and application of molecular switching devices. This overview offers valuable insights into the switching mechanisms under various stimuli, emphasizing structural and energy state changes in the core molecules. Beyond the molecular switches, typical individual metal atomic switches are further introduced. A critical discussion of the main challenges for realizing and developing practical molecular/atomic switches is provided. These analyses and summaries will contribute to a comprehensive understanding of the switch mechanisms, providing guidance for the rational design of functional nanoswitch devices toward practical applications.

Tunable and enhanced thermoelectric properties in transition metal–terpyridine complex based molecular devices

Using the density function theory in combination with the non-equilibrium Green’s function method, the thermoelectric properties of molecular devices based on transition metal–terpyridine complexes are investigated. The results show that their thermoelectric properties can be significantly improved by changing the transition metal and the twist angle of the complex molecule, which is caused by shifting the molecular energy levels, resulting in increased coupling strength between the electrodes and the central molecule. The ZT value of the Ru-containing molecular device can reach up to 0.9 at room temperature, which is three orders of magnitude greater than that of the graphene nanoribbons of the same width. In addition, its thermoelectric performance can be further promoted by suppressing phonon thermal conductance through enhanced isotope scattering. The ZT value of doped devices can reach up to 1.0 in the range of 300–700 K. This work may help in the design and fabrication of transition metal-containing twistable molecular devices and provide effective methods to regulate their thermoelectric properties.

Temperature Induced Reversible Switching of the Magnetic Anisotropy in a Neodymium Complex Adsorbed on Graphite.

Controlling the magnetic anisotropy of molecular layers assembled on a surface is one of the challenges that needs to be addressed to create the next-generation spintronic devices. Recently, metal complexes that show a reversible solid-state switch of their magnetic anisotropy in response to physical stimuli, such as temperature and magnetic field, have been discovered. The complex Nd(trensal) (H3trensal=2,2',2''-tris(salicylideneimino)triethylamine) is predicted to exhibit such property. An ultra-thin film of Nd(trensal) is deposited on highly ordered pyrolytic graphite as a proof-of-concept system to show that this property can be retained at the nanoscale on a layered material. By combining single crystal magnetometric measurements and synchrotron X-ray-based absorption techniques, supported by multiplet ligand field simulations based on the trigonal crystal field surrounding the lanthanide centre, it is demonstrated that changing the temperature reverses the magnetic anisotropy of an ordered film of Nd(trensal), thus opening significant perspectives for the realization of a novel family of temperature-controlled molecular spintronic devices.

Development of an FeII Complex Exhibiting Intermolecular Proton Shifting Coupled Spin Transition.

In this study, we investigated reversible intermolecular proton shifting (IPS) coupled with spin transition (ST) in a novel FeII complex. The host FeII complex and the guest carboxylic acid anion were connected by intermolecular hydrogen bonds (IHBs). We extended the intramolecular proton transfer coupled ST phenomenon to the intermolecular system. The dynamic phenomenon was confirmed by variable-temperature single-crystal X-ray diffraction, neutron crystallography, and infrared spectroscopy. The mechanism of IPS was further validated using density functional theory calculations. The discovery of IPS-coupled ST in crystalline molecular materials provides good insights into fundamental processes and promotes the design of novel multifunctional materials with tunable properties for various applications, such as optoelectronics, information storage, and molecular devices.

Development of an FeII Complex Exhibiting Intermolecular Proton Shifting Coupled Spin Transition

AbstractIn this study, we investigated reversible intermolecular proton shifting (IPS) coupled with spin transition (ST) in a novel FeII complex. The host FeII complex and the guest carboxylic acid anion were connected by intermolecular hydrogen bonds (IHBs). We extended the intramolecular proton transfer coupled ST phenomenon to the intermolecular system. The dynamic phenomenon was confirmed by variable‐temperature single‐crystal X‐ray diffraction, neutron crystallography, and infrared spectroscopy. The mechanism of IPS was further validated using density functional theory calculations. The discovery of IPS‐coupled ST in crystalline molecular materials provides good insights into fundamental processes and promotes the design of novel multifunctional materials with tunable properties for various applications, such as optoelectronics, information storage, and molecular devices.

Giant magneto-photoluminescence at ultralow field in organic microcrystal arrays for on-chip optical magnetometer

Optical detection of magnetic field is appealing for integrated photonics; however, the light-matter interaction is usually weak at low field. Here we observe that the photoluminescence (PL) decreases by > 40% at 10 mT in rubrene microcrystals (RMCs) prepared by a capillary-bridge assembly method. The giant magneto-PL (MPL) relies on the singlet-triplet conversion involving triplet-triplet pairs, through the processes of singlet fission (SF) and triplet fusion (TF) during radiative decay. Importantly, the size of RMCs is critical for maximizing MPL as it influences on the photophysical processes of spin state conversion. The SF/TF process is quantified by measuring the prompt/delayed PL with time-resolved spectroscopies, which shows that the geminate SF/TF associated with triplet-triplet pairs are responsible for the giant MPL. Furthermore, the RMC-based magnetometer is constructed on an optical chip, which takes advantages of remarkable low-field sensitivity over a broad range of frequencies, representing a prototype of emerging opto-spintronic molecular devices.

Integrating spin-dependent emission and dielectric switching in FeII catenated metal-organic frameworks

Mechanically interlocked molecules (MIMs) including famous catenanes show switchable physical properties and attract continuous research interest due to their potential application in molecular devices. The advantages of using spin crossover (SCO) materials here are enormous, allowing for control through diverse stimuli and highly specific functions, and enabling the transfer of the internal dynamics of MIMs from solution to solid state, leading to macroscopic applications. Herein, we report the efficient self-assembly of catenated metal-organic frameworks (termed catena-MOFs) induced by stacking interactions, through the combination of rationally selected flexible and conjugated naphthalene diimide-based bis-pyridyl ligand (BPND), [MI(CN)2]− (M = Ag or Au) and Fe2+ in a one-step strategy. The obtained bimetallic Hofmann-type SCO-MOFs [FeII(BPND){Ag(CN)2}2]·3CHCl3 (1Ag) and [FeII(BPND{Au(CN)2}2]·2CHCl3·2H2O (1Au) possess a unique three-dimensional (3D) catena-MOF constructed from the polycatenation of two-dimensional (2D) layers with hxl topology. Both complexes undergo thermal- and light-induced SCO. Significantly, abnormal increases in the maximum emission intensity and dielectric constant can be detected simultaneously with the switching of spin states. This research opens up SCO-actuated bistable MIMs that afford dual functionality of coupled fluorescence emission and dielectricity.

A violet light-emitting diode-based gas-phase molecular absorption device for measurement of nitrate and nitrite in environmental water

A simple and sensitive device for the detection of nitrite and nitrate in environmental waters was developed based on visible light gas-phase molecular absorption spectrometry. By integrating a detection cell (DC), semiconductor refrigeration temperature-controlling system (SRTCY), and nitrite reactor into a sequential injection analysis system, trace levels of nitrite and nitrate in complex matrices were successfully measured. A low energy-consuming light-emitting diode (violet, 400–405 nm) was coupled with a visible light-to-voltage converter (TSL257) to measure the gas-phase molecular absorption. To reduce the interference of water vapor, an SRTCY was used to condense the water vapor on-line before the gas-phase analyte entered the DC. The DC was radiatively heated by the SRTCY to avoid water vapor condensation in the light path. As a result, the obtained baseline noise reduced 3.75 times than that of without SRTCY. Under the optimized conditions, the device achieved limits of detection (3σ/k) of 0.055 and 0.36 mmol/L (0.77 and 5.04 mg N/L) for nitrite and nitrate, respectively, and the linear calibration ranges were 0.1–15 mmol/L (R2 = 0.9946) and 1–10 mmol/L (R2 = 0.9995), respectively. Precisions of 5.2 % and 9.0 % were achieved for ten successive determinations of 0.3 mmol/L nitrite and 1.0 mmol/L nitrate, and the analytical times for nitrite and nitrate determination were 5 and 13 min, respectively. This method was validated against standard methods and recovery tests, and it was applied to the measurement of nitrite and nitrate in environmental waters. Moreover, a device was designed to enable the field measurement of nitrite and nitrate in complex matrices.

Exploring the Odd–Even Effect, Current Stabilization, and Negative Differential Resistance in Carbon-Chain-Based Molecular Devices

The transport properties of molecular devices based on carbon chains are systematically investigated using a combination of non-equilibrium Green’s function (NEGF) and density functional theory (DFT) first-principle methods. In single-carbon-chain molecular devices, a distinct even–odd behavior of the current emerges, primarily influenced by the density of states (DOS) within the chain channel. Additionally, linear, monotonic currents exhibit Ohmic contact characteristics. In ladder-shaped carbon-chain molecular devices, a notable current stabilization behavior is observed, suggesting their potential utility as current stabilizers within circuits. We provide a comprehensive analysis of the transport properties of molecular devices featuring ladder-shaped carbon chains connecting benzene-ring molecules. The occurrence of negative differential resistance (NDR) in the low-bias voltage region is noted, with the possibility of manipulation by adjusting the position of the benzene-ring molecule. These findings offer a novel perspective on the potential applications of atom chains.

Restricting Conformational Space: A New Blueprint for Electrically Switchable Self-Assembled Monolayers.

Tunnel junctions comprising self-assembled monolayers (SAMs) from liquid crystal-inspired molecules show a pronounced hysteretic current-voltage response, due to electric field-driven dipole reorientation in the SAM. This renders these junctions attractive device candidates for emerging technologies such as in-memory and neuromorphic computing. Here, the novel molecular design, device fabrication, and characterization of such resistive switching devices with a largely improved performance, compared to the previously published work are reported. Those former devices suffer from a stochastic switching behavior limiting reliability, as well as from critically small read-out currents. The present progress is based on replacing Al/AlOx with TiN as a new electrode material and as a key point, on redesigning the active molecular material making up the SAM: a previously present, flexible aliphatic moiety has been replaced by a rigid aromatic linker, thereby introducing a molecular "ratchet". This restricts the possible molecular conformations to only two major states of opposite polarity. The above measures have resulted in an increase of the current density by five orders of magnitude as well as in an ON/OFF conductance ratio which is more than ten times higher than the individual scattering ranges of the high and low resistance states.

Hypoxia Alters Sympathetic Terminal Function and Innervation Patterns in the Rat Left Atrium

Atrial fibrillation (AF) is the most common sustained cardiac arrhythmia (Hindricks et al., 2021). Emerging evidence suggests that the association of AF with conditions such as obstructive sleep apnoea, COPD and heart failure may be partly attributable to atrial autonomic remodelling in the setting of chronic hypoxia (CH) and chronic-intermittent hypoxia (CIH) (Saleeb-Mousa et al. 2023). In particular, hypoxic remodelling of the atrial autonomic system is associated with a shift towards sympathetic predominance. We hypothesised that sympathetic remodelling in CH and CIH is characterised by altered regulation of prejunctional terminal function. Procedures were performed in accordance with the UK Animals (Scientific Procedures) Act 1986. A novel confocal fluorescence assay was employed to dynamically monitor single-terminal noradrenaline handling in vitro (Cao et al. 2020). This technique utilises the neurotransmitter transporter uptake assay (NTUA, Molecular Devices), a fluorescent monoamine mimetic which accumulates in sympathetic terminals by entering via the noradrenaline transporter (NAT). Experiments were performed in atrial tissues derived from male adult Wistar rats (200-300g) kept in normoxia (N; n=24), CH (FIO2=0.1-0.12, 9-10 days; n=9) and CIH (FIO2=0.06-0.21, 15 cycles hour−1, 8 hours day−1, 21-24 days; n=4) using a hypoxia chamber. Hearts were excised under non-recovery terminal inhalation isoflurane (3-5% in O2, flow rate 1.5L min−1) with death by cervical dislocation. Tissues were dissected into left atrial appendage (LAA), left atrial posterior wall (LAPW), right atrium (RA), right atrial appendage (RAA) and pulmonary veins. Sections were pinned flat and transferred to a confocal microscope. Tissues were superfused with NTUA and images were captured over 15 minutes to allow for quantification of fluorescence uptake. To determine innervation density, additional imaging of NTUA-loaded tissues was performed at low magnification in each region. Further structural images were captured in an additional group of rats (nN=2, nCH=6) using an anterograde tracing technique. Tissues were excised with sympathetic chains intact, and a dextran-conjugated fluorophore (Dextran Texas Red, Invitrogen) was loaded over 21 hours into either the left or right stellate ganglion. Tissues were subsequently dissected and confocal imaging was performed to visualise atrial sympathetic fibres. Analysis of fluorescence uptake in all tissues revealed a two-phase association characterized by an initial 6-minute linear uptake followed by a plateau phase. In preliminary CIH experiments, no significant changes in NTUA uptake were observed (p>0.05). In CH tissues, linear uptake was not significantly different compared with N (p=0.09). CH was associated with an increase in maximum fluorescence (p=0.0004); however, a significant effect was only observed in the LAA (p=0.008). CH tissues also demonstrated a sympathetic hyperinnervation (p<0.0001), with post-hoc testing revealing a significant effect in the LAPW (p=0.0007). Stellate tracing in all animals revealed diffuse innervation of the LAPW, but an absence of fluorescence in the RA, LAA and RAA. Overall, our data demonstrate regionally dependent functional and structural adaptations of the cardiac sympathetic system to hypoxia. Further work should aim to determine the contribution of atrial autonomic heterogeneity to arrhythmogenesis in conditions associated with CH. This research was funded by the Kennedy Trust, grant number KENN 20 21 04-Saleeb-Mousa, and the British Heart Foundation, grant number FS/PhD/20/29093. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

Theoretical study of the ϒ2-graphyne p-n junction diode devices

Due to the tunable bandgap of ϒ2-graphyne, there is an expectation that this structure is a favorable candidate for p-n junction diode devices. The characteristic of the pure and hydrogenated ϒ2-graphyne nanoribbon structures is modeled and investigated from the electrostatic point of view. The charge distribution is approximated in one and two dimensions. The space charge region wide, electric field and the potential along with the current density are calculated for different donor and acceptor doping amounts. Our survey includes various simulated hydrogenated and Oxygenated molecular devices with different unit cell numbers, and their density of states, transmission spectrum, and current voltage diagrams were obtained using VNL Quantum wise ATK software. The results indicate the reduction of the depletion region and the creation of new energy levels in the band gap of the system. The interaction and bending effects of these new levels with the intrinsic levels are also observed.