Detection of a Chirality-Induced Spin Selective Quantum Capacitance in α-Helical Peptides.

Advanced Kelvin probe force microscopy simultaneously detects the quantum capacitance and surface potential of an α-helical peptide monolayer. These indicators shift when either the magnetic polarization or the enantiomer is toggled. A model based on a triangular quantum well in thermal and chemical equilibrium and electron-electron interactions allows for calculating the electrical potential profile from the measured data. The combination of the model and the measurements shows that no global charge transport is required to produce effects attributed to the chirality-induced spin selectivity effect. These experimental findings support the theoretical model of Fransson et al. Nano Letters 2021, 21 (7), 3026-3032. Measurements of the quantum capacitance represent a new way to test and refine theoretical models used to explain strong spin polarization due to chirality-induced spin selectivity.

Ligand-Mediated Nanocrystal Growth.

A microfluidic platform combined with a deterministic model accounting for surface ligands reveals precious insights into the nanocrystal formation process. The comparison of on-line kinetic information with model predictions enables the derivation of temperature-dependent kinetic parameters for the CdSe model system. This fully generalizable approach represents a step forward toward a quantitative prediction of the nanocrystal size distribution, enabling the control and optimization of process performance and material properties.

Monitoring the transformation of aliphatic and fullerene molecules by high-energy electrons using surface-enhanced Raman spectroscopy.

We report on using 100 keV electrons to obtain amorphous carbon from aliphatic and fullerene molecules, and study this process by monitoring their Raman signal. In this regard, we use self-assembled monolayers of gold nanoparticles to provide high electromagnetic field enhancement, which allows the detection of the Raman signal from even nanometer-thick layers of analyte. Our results show different dynamics in the amorphization process of the two molecules, although both show suppression of their original vibrational resonances even at low exposure doses. We have also used atomic-force microscopy to evaluate the sensitivity of the C60 molecules to electron beams in forming networks of amorphized molecules that are less soluble in the development process. This method allows precise patterning possibilities as well as in situ functionalization of carbonaceous thin films in the perspective of using in electronic device applications.

Resistive switching of alkanethiolated nanoparticle monolayers patterned by electron-beam exposure.

Carbon-based electronic devices are promising candidates for complementing silicon-based electronics in memory device applications. For example, sputtered thin films of amorphous carbon exhibit memristive behavior. The reported devices, however, have a minimal active area of about 50 nm diameter, leading to large set currents in the µA range. Although power efficiency would benefit from reduced drive currents, resistive switching of amorphous carbon confined to a few cubic nanometers has remained largely unexplored. Here, we investigate resistive switching in 30 nm long and 25 nm wide monolayer arrays of 10 nm gold nanoparticles patterned by direct electron-beam exposure followed by a purpose-designed emulsion-based development process. Electron-beam irradiation transforms the alkanethiol ligands of the gold nanoparticles into a solvent-resistant amorphous carbonaceous matrix allowing pattern development and imparting electronic function. We measure changes in conductivity of up to five orders of magnitude for set currents in the nA range.

Water-Mediated Assembly of Gold Nanoparticles into Aligned One-Dimensional Superstructures.

This Article shows that water in ethanol colloids of gold nanoparticles enhances the formation of linear clusters and, more important for applications in electronics, determines their assembly on surfaces. We show by dynamic light scattering that ethanol colloids contain mainly monomers and dimers and that wormlike superstructures are mostly absent, despite UV-vis evidence of aggregation. Water added to the colloid as a cosolvent was found to enhance the number of clusters as well as their average size, confirming its role in linear self-assembly, on the scale of a few particles. Water adsorbed from the atmosphere during coating was also found to be a powerful lever to tune self-assembly on surfaces. By varying the relative humidity, a sharp transition from branched to linear superstructures was observed, showing the importance of water as a cosolvent in the formation of cluster superstructures. We show that one-dimensional superstructures may form due to long-range mobility of precursor clusters on wet surfaces, allowing their rearrangement. The understanding of the phenomenon allows us to statistically align both clusters and resulting superstructures on patterned substrates, opening the way to rapid screening in molecular electronics.

Contact transfer length investigation of a 2D nanoparticle network by scanning probe microscopy.

Nanoparticle network devices find growing application in sensing and electronics. One recurring challenge in the design and fabrication of this class of devices is ensuring a stable interface via robust yet unobstructive electrodes. A figure of merit which dictates the minimum electrode overlap required for optimal charge injection into the network is the contact transfer length. However, we find that traditional contact characterization using the transmission line model, an indirect method which requires extrapolation, is insufficient for network devices. Instead, we apply Kelvin probe force microscopy to characterize the contact resistance by imaging the surface potential with nanometer resolution. We then use scanning probe lithography to directly investigate the contact transfer length. We have determined the transfer length in graphene contacted devices to be 200-400 nm, thus apt for further device reduction which is often necessary for on-site sensing applications. Simulations from a two-dimensional resistor model support our observations and are expected to be an important tool for further optimizing the design of nanoparticle-based devices.

An in vitro method to investigate the microbicidal potential of human macrophages for use in psychosomatic research.

OBJECTIVE: Psychological states relate to changes in circulating immune cells, but associations with immune cells in peripheral tissues such as macrophages have hardly been investigated. Here, we aimed to implement and validate a method for measuring the microbicidal potential of ex vivo isolated human monocyte-derived macrophages (HMDMs) as an indicator of macrophage activation. METHODS: The method was implemented and validated for two blood sampling procedures (short-term cannula insertion versus long-term catheter insertion) in 79 participants (34 women, 45 men) aged between 18 and 75 years. The method principle is based on the reduction of 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-dis-ulfophenyl)-2H-tetrazolium, monosodium salt (WST-1) by superoxide anions, the first in a series of pathogen-killing reactive oxygen species produced by phorbol myristate acetate-activated HMDM. Cytochrome c reduction and current generation were measured as reference methods for validation purposes. We further evaluated whether depressive symptom severity (Beck Depression Inventory) and chronic stress (Chronic Stress Screening Scale) were associated with macrophage microbicidal potential. RESULTS: The assay induced superoxide anion responses by HMDM in all participants. Assay results depended on blood sampling procedure (cannula versus catheter insertion). Interassay variability as a measure for assay reliability was 10.92% or less. WST-1 reduction scores correlated strongly with results obtained by reference methods (cytochrome c: r = 0.57, p = .026; current generation: r values ≥ 0.47, p values <.033) and with psychological factors (depressive symptom severity: r = 0.35 [cannula insertion] versus r = -0.54 [catheter insertion]; chronic stress: r = 0.36 [cannula insertion]; p values ≤ .047). CONCLUSIONS: Our findings suggest that the implemented in vitro method investigates microbicidal potential of HMDM in a manner that is valid and sensitive to psychological measures.

Thermal transport into graphene through nanoscopic contacts.

Superior thermal conductivity of graphene is frequently reported and used to justify its technical relevance for ultimately scaled devices. However, this extraordinary property is size dependent, and understanding of graphene's thermal properties in the quasiballistic thermal transport regime is lacking. To overcome this limitation, we directly probe local heat transfer into graphene by high-resolution scanning thermal microscopy on amorphous silicon oxide (SiO2) and crystalline silicon carbide (SiC). We quantify thickness-dependent thermal resistance modulations at sub-10-nm lateral resolution and thermal sensitivity for the individual atomic layers. On SiO2, we observe a decrease of thermal resistance with increasing number of graphene layers. We attribute this trend to the spreading of heat using the thickness dependence of graphene's thermal conductivity. On SiC, the heated tip-sample contact is scaled below the phonon mean free path of both the graphene and its supporting substrate. Consistently, we find the thermal interface resistances of the graphene top and bottom contacts dominating thermal transport.

Square-micrometer-sized, free-standing organometallic sheets and their square-centimeter-sized multilayers on solid substrates.

Oligofunctional terpyridine-based monomers are spread at an air/water interface, where they are connected with transition metal salts such as Fe(II) into mechanically coherent monolayer sheets of macroscopic dimension. The conversions of these processes are determined by XPS for several monomer/metal ion combinations. The sheets are transferred onto TEM grids, the 20 × 20 square micrometer sized holes of which can be spanned. AFM indentation experiments provide in-plane elastic moduli which are compared with naturally occurring sheets such as graphene. The new organometallic sheets are also used to create multilayer assemblies on square centimeter length scales on solid substrates. Finally some directions are provided where this research can lead to in future and where its application potential lies.

Quantitative thermometry of nanoscale hot spots.

A method is described to quantify thermal conductance and temperature distributions with nanoscale resolution using scanning thermal microscopy. In the first step, the thermal resistance of the tip-surface contact is measured for each point of a surface. In the second step, the local temperature is determined from the difference between the measured heat flux for heat sources switched on and off. The method is demonstrated using self-heating of silicon nanowires. While a homogeneous nanowire shows a bell-shaped temperature profile, a nanowire diode exhibits a hot spot centered near the junction between two doped segments.

CVD of MoS2 single layer flakes using Na2MoO4 - impact of oxygen and temperature-time-profile.

Two-dimensional (2D) materials are of great interest in many fields due to their astonishing properties at an atomic level thickness. Many fundamentally different methods to synthesize 2D materials, such as exfoliation or chemical vapor deposition (CVD), have been reported. Despite great efforts and progress to investigate and improve each synthesis method, mainly to increase the yield and quality of the synthesized 2D materials, most approaches still involve some compromise. Herein, we systematically investigate a chemical vapor deposition (CVD) process to synthesize molybdenum disulfide (MoS2) single layer flakes using sodium molybdate (Na2MoO4), deposited on a silica (SiO2/Si) substrate by spin-coating its aqueous solution, as the molybdenum source and sulfur powder as sulfur source, respectively. The focus lies on the impact of oxygen (O2) in the gas flow and temperature-time-profile on reaction process and product quality. Atomic force microscopy (AFM), Raman and photoluminescence (PL) spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to investigate MoS2 flakes synthesized under different exposure times of O2 and with various temperature-time-profiles. This detailed study shows that the MoS2 flakes are formed within the first few minutes of synthesis and elaborates on the necessity of O2 in the gas flow, as well as drawbacks of its presence. In addition, the applied temperature-time-profile highly affects the ability to detach MoS2 flakes from the growth substrate when immersed in water, but it has no impact on the flake.

Tunable Subnanometer Gaps in Self-Assembled Monolayer Gold Nanoparticle Superlattices Enabling Strong Plasmonic Field Confinement.

Nanoparticle superlattices produced with controllable interparticle gap distances down to the subnanometer range are of superior significance for applications in electronic and plasmonic devices as well as in optical metasurfaces. In this work, a method to fabricate large-area (∼1 cm2) gold nanoparticle (GNP) superlattices with a typical size of single domains at several micrometers and high-density nanogaps of tunable distances (from 2.3 to 0.1 nm) as well as variable constituents (from organothiols to inorganic S2-) is demonstrated. Our approach is based on the combination of interfacial nanoparticle self-assembly, subphase exchange, and free-floating ligand exchange. Electrical transport measurements on our GNP superlattices reveal variations in the nanogap conductance of more than 6 orders of magnitude. Meanwhile, nanoscopic modifications in the surface potential landscape of active GNP devices have been observed following engineered nanogaps. In situ optical reflectance measurements during free-floating ligand exchange show a gradual enhancement of plasmonic capacitive coupling with a diminishing average interparticle gap distance down to 0.1 nm, as continuously red-shifted localized surface plasmon resonances with increasing intensity have been observed. Optical metasurfaces consisting of such GNP superlattices exhibit tunable effective refractive index over a broad wavelength range. Maximal real part of the effective refractive index, nmax, reaching 5.4 is obtained as a result of the extreme field confinement in the high-density subnanometer plasmonic gaps.

Local strain and tunneling current modulate excitonic luminescence in MoS2 monolayers.

The excitonic luminescence of monolayer molybdenum disulfide (MoS2) on a gold substrate is studied by scanning tunneling microscopy (STM). STM-induced light emission (STM-LE) from MoS2 is assigned to the radiative decay of A and B excitons. The intensity ratio of A and B exciton emission is modulated by the tunneling current, since the A exciton emission intensity saturates at high tunneling currents. Moreover, the corrugated gold substrate introduces local strain to the monolayer MoS2, resulting in significant changes of electronic bandgap and valence band splitting. The modulation rate of strain on A exciton energy is estimated as -69 ± 5 meV/%. STM-LE provides a direct link between exciton energy and local strain in monolayer MoS2 on a length scale of 10 nm.

Force gradient sensitive detection in lift-mode Kelvin probe force microscopy.

We demonstrate frequency modulation Kelvin probe force microscopy operated in lift-mode under ambient conditions. Frequency modulation detection is sensitive to force gradients rather than forces as in the commonly used amplitude modulation technique. As a result there is less influence from electric fields originating from the tip's cone and cantilever, and the recorded surface potential does not suffer from the large lateral averaging observed in amplitude modulated Kelvin probe force microscopy. The frequency modulation technique further shows a reduced dependence on the lift-height and the frequency shift can be used to map the second order derivative of the tip-sample capacitance which gives high resolution material contrast of dielectric sample properties. The sequential nature of the lift-mode technique overcomes various problems of single-scan techniques, where crosstalk between the Kelvin probe and topography feedbacks often impair the correct interpretation of the recorded data in terms of quantitative electric surface potentials.

Carbon-coated magnetic nanoparticles as a removable protection layer extending the operation lifetime of bilirubin oxidase-based bioelectrode.

One of the factors hindering the development of enzymatic biosensors and biofuel cells in real-life applications is the time-dependant degradation of the biocatalysts on electrode surfaces. In this work, we present a new practical approach for extending the operation lifetimes of bioelectrocatalytic assemblies based on bilirubin oxidase (BOD). As evident by both spectroscopic and electrochemical measurements, an adsorption of carbon-coated magnetic nanoparticles (ccMNPs) onto a BOD/carbon nanotubes-deposited surface yields a stable bioelectrocathode system for mediatorless oxygen reduction. As compared to electrodes, which were stored without a preliminary interaction with the ccMNPs, an 80% increase in the active enzymatic content and the electrocatalytic performance was evident for the modified assemblies over a course of one month. As the full removal of the protective particles before the measurement requires only a single step applying an external magnetic force, the method is shown to be simple, reproducible, and easy to implement. Combined with the high efficiency in preserving the enzymatic stability and bioelectrocatalytic currents, the findings suggest a promising methodology for enhancing the lifetimes of bioelectronic applications.

Measurement of electrostatic tip-sample interactions by time-domain Kelvin probe force microscopy.

Kelvin probe force microscopy is a scanning probe technique used to quantify the local electrostatic potential of a surface. In common implementations, the bias voltage between the tip and the sample is modulated. The resulting electrostatic force or force gradient is detected via lock-in techniques and canceled by adjusting the dc component of the tip-sample bias. This allows for an electrostatic characterization and simultaneously minimizes the electrostatic influence onto the topography measurement. However, a static contribution due to the bias modulation itself remains uncompensated, which can induce topographic height errors. Here, we demonstrate an alternative approach to find the surface potential without lock-in detection. Our method operates directly on the frequency-shift signal measured in frequency-modulated atomic force microscopy and continuously estimates the electrostatic influence due to the applied voltage modulation. This results in a continuous measurement of the local surface potential, the capacitance gradient, and the frequency shift induced by surface topography. In contrast to conventional techniques, the detection of the topography-induced frequency shift enables the compensation of all electrostatic influences, including the component arising from the bias modulation. This constitutes an important improvement over conventional techniques and paves the way for more reliable and accurate measurements of electrostatics and topography.

Simplified approach to diffraction tomography in optical microscopy.

We present a novel microscopy technique to measure the scattered wavefront emitted from an optically transparent microscopic object. The complex amplitude is decoded via phase stepping in a common-path interferometer, enabling high mechanical stability. We demonstrate theoretically and practically that the incoherent summation of multiple illumination directions into a single image increases the resolving power and facilitates image reconstruction in diffraction tomography. We propose a slice-by-slice object-scatter extraction algorithm entirely based in real space in combination with ordinary z-stepping. Thereby the computational complexity affiliated with tomographic methods is significantly reduced. Using the first order Born approximation for weakly scattering objects it is possible to obtain estimates of the scattering density from the exitwaves.

Power Generation by Selective Self-Assembly of Biocatalysts.

Through a careful chemical and bioelectronic design we have created a system that uses self-assembly of enzyme-nanoparticle hybrids to yield bioelectrocatalytic functionality and to enable the harnessing of electrical power from biomass. Here we show that mixed populations of hybrids acting as catalyst carriers for clean energy production can be efficiently stored, self-assembled on functionalized stationary surfaces, and magnetically re-collected to make the binding sites on the surfaces available again. The methodology is based on selective interactions occurring between chemically modified surfaces and ligand-functionalized hybrids. The design of a system with minimal cross-talk between the particles, outstanding selective binding of the hybrids at the electrode surfaces, and direct anodic and cathodic electron transfer pathways leads to mediator-less bioelectrocatalytic transformations which are implemented in the construction of a fast self-assembling, membrane-less fructose/O2 biofuel cell.

Enzymatic self-wiring in nanopores and its application in direct electron transfer biofuel cells.

A synthetic enzymatic activity in nanopores leading to the direct fabrication of modified electrodes applicable as biosensors and/or biofuel cell elements is reported. We demonstrate the heterogeneous enzymatic implanting of platinum nanoclusters, PtNCs, in glucose oxidase, GOx, immobilized on mesoporous carbon nanoparticles, MPCNP-modified surface. As the pores confine the growth of the clusters, the PtNC@GOx/MPCNP assembly becomes electrically wired to the matrix, demonstrating direct electron transfer, DET, bioelectrocatalytic properties that correlate with the applied duration of synthesis and cluster size. This inside-out nanocluster growth from the cofactor to the matrix is investigated and further compared to a reversed outside-in strategy which follows the electrochemical deposition of the Pt clusters inside the pores and their electrically induced expansion towards the FAD center of the enzyme. While the inside-out and outside-in methodologies provide, for the first time, synthetic bidirectional direct wiring routes of an enzyme to a surface, we highlight an asymmetry in the wiring efficiency associated with the different assemblies. The results indicate the existence of a shorter gap between the FAD cofactor and the PtNCs in the enzymatically implanted assembly, resulting in elevated bioelectrocatalytic currents, lower overpotential, and a higher turnover rate, 2580 e- s-1. The implanted assembly is then coupled to a bilirubin oxidase-adsorbed MPCNP cathode to yield an all-DET biofuel cell. Due to the superior electrical contact of the inside-out-synthesized anode, this cell demonstrates enhanced discharge potential and power outputs as compared to similar systems employing electrochemically synthesized outside-in-grown PtNC-GOx/MPCNPs or even GOx-modified MPCNPs diffusionally mediated by ferrocenemethanol.

Magnetically induced enzymatic cascades - advancing towards multi-fuel direct/mediated bioelectrocatalysis.

A generic method to magnetically assemble enzymatic cascades on electrode surfaces is introduced. The versatile method enables the simultaneous activation of both direct and mediated electron transfer bioelectrocatalysis to harness different substrates, which can serve as multiple fuels and oxidizers in biofuel cells generating clean energy.