Electro-Chemo-Mechanically Stable and Sodiophilic Interface for Na Metal Anode in Liquid-based and Solid-State Batteries.

Na metal batteries (NMBs) are attracting increasing attention because of their high energy density. However, the widespread application of NMBs is hindered by the growth of Na dendrites and interface instability. The design of artificial solid electrolyte interphase (SEI) with tuned chemical/electrochemical/mechanical properties is the key to achieving high-performance NMBs. This work develops a metal-doped nanoscale polymeric film with tunable composition, sodiophilic sites and improved stiffness. The incorporation of metal crosslinkers in the polymer chains results in exceptional electrochemical stability for Na metal anodes, leading to a significantly prolonged lifespan even at high current densities, which is at the top of the reported literature. The mechanical properties measurements and electro-chemo-mechanical phase-field model are performed to interpret the impact of the ionic transportation capability (decoupled mechanical) and mechanic property in the metal-doped polymer interface. In addition, this approach provides a promising strategy for the rational design of electrode interfaces, providing enhanced mechanical stability and improved sodiophilicity, which can open up opportunities for the fabrication of next-generation energy storage.

Analytical strategies to identify multicomponent quality markers for commercial Hua-ju-hong using multidimensional chemical analysis.

Hua-ju-hong (HJH) is a Chinese medicinal material obtained from Citrus grandis 'Tomentosa' (CGT) and Citrus grandis (L.) Osbeck (CG) with various commercial specifications. It is known for relieving cough and dispelling phlegm. To reveal the quality marker for distinguishing the various HJH, 215 batches of commercial HJH were studied systematically using multidimensional chemical analysis. Ten major components were identified by high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry and quantified via high-performance liquid chromatography coupled with diode array detection. In this study, a rapid, efficient, and low-cost chromatographic method was established. Total coumarin-hemiterpene and total coumarin-monoterpene were first classified and analyzed in HJH. The result indicated that the main component, naringin, was not the quality marker for differentiating CGT from CG. For reflecting the unique medicinal and food value of HJH, coumarins should be the more potential quality markers. Flavonoids were the possible quality markers for distinguishing two growth stages of fruit-exocarp and young fruit. For the first time, two chemotypes of HJH were identified in CG. This study provides a convenient yet reliant chromatographic method and novel yet systematic strategies for overall quality control of commercial HJH.

Development of a Bio-Hybrid Mosquito Stinger-Based Atomic Force Microscopy Probe.

Mosquitoes, notorious as the deadliest animals to humans due to their capacity to transmit diseases, pose a persistent challenge to public health. The primary prevention strategy currently in use involves chemical repellents, which often prove ineffective as mosquitoes rapidly develop resistance. Consequently, the invention of new preventive methods is crucial. Such development hinges on a thorough understanding of mosquito biting behaviors, necessitating an experimental setup that accurately replicates actual biting scenarios with controllable testing parameters and quantitative measurements. To bridge this gap, a bio-hybrid atomic force microscopy (AFM) probe was engineered, featuring a biological stinger - specifically, a mosquito labrum - as its tip. This bio-hybrid probe, compatible with standard AFM systems, enables a near-authentic simulation of mosquito penetration behaviors. This method marks a step forward in the quantitative study of biting mechanisms, potentially leading to the creation of effective barriers against vector-borne diseases (VBDs) and opening new avenues in the fight against mosquito-transmitted illnesses.

Low-Profile, Large-Range Compressive Strain Sensing Using Micromanufactured CNT Micropillar Arrays.

Tactile sensors, or sensors that collect measurements through touch, have versatile applications in a wide range of fields including robotic gripping, intelligent manufacturing, and biomedical technology. Hoping to match the ability of human hands to sense physical changes in objects through touch, engineers have experimented with a variety of materials from soft polymers to hard ceramics, but so far, all have fallen short. A grand challenge for developers of "human-like" bionic tactile sensors is to be able to sense a wide range of strains while maintaining the low profile necessary for compact integration. Here, we developed a low-profile tactile sensor (∼300 µm in height) based on patterned, vertically aligned carbon nanotubes (PVACNT) that can repetitively sense compressive strains of up to 75%. Upon compression, reversible changes occur in the points of contact between CNTs, producing measurable changes in electrical admittance. By patterning VACNT pillars with different aspect ratios and pitch sizes, we engineered the range and resolution of strain sensing, suggesting that CNT-based tactile sensors can be integrated according to device specifications.

Controlling strong-field fragments of HD+ with a synthesized two-color laser pulse.

The possibility of controlling fragment branching in the dissociation and ionization channels of HD+ is theoretically explored by synthesized intense fields using 790 nm and 395 nm pulses. In the control scheme, the branching ratios of the fragments to different channels (H + D+, D + H+ and H+ + D+) are manipulated by regulating the relative phase and intensity between the 790 nm and 395 nm pulses. Altering the relative phase can induce constructive or destructive interference between the net two photon process and the direct one photon process, and the highest modulation reaches 80% between the two dissociation fragments (H + D+ and D + H+). The high selectivity of the ionization fragment (H+ + D+) is achieved by tuning the relative intensity, since the ionization rate is not only related to the internuclear distance, but also to the instantaneous intensity of field strength. The results demonstrate that the synthesized ω-2ω laser pulse can provide an efficient control over the strong-field fragments of HD+.

Printed flexible mechanical sensors.

Flexible mechanical sensors (e.g., strain, pressure, and force) fabricated primarily by printing technologies have emerged and evolved promptly in the past several years. 2D and 3D printing approaches enabled rapid prototyping of various flexible mechanical sensors that have demonstrated their unique applications in fields including robotics, human-machine interfaces, and biomedicine. Research efforts have primarily been focused on experimenting with different materials, device configurations, and sensing mechanisms to achieve better sensing performance. While great progress has been made, this field is still in its infancy where most research is exploratory; and even the performance standards and long-term objective/vision of these sensors are not clear. In this review, the state-of-the-art of three types of printed flexible mechanical sensors will be discussed and analyzed in terms of their fabrication methods, types of sensing materials and mechanisms, and challenges for future development.

Multiscale Plasmonic Refractory Nanocomposites for High-Temperature Solar Photothermal Conversion.

Development of a refractory selective solar absorber (RSSA) is the key to unlock high-temperature solar thermal and thermochemical conversion. The fundamental challenge of RSSA is the lack of design and fabrication guidelines to simultaneously achieve omnidirectional, broadband solar absorption and sharp spectral selectivity at the desired cutoff wavelength. Here, we realize a ruthenium-carbon nanotube (Ru-CNT) nanocomposite RSSA with multiscale nanoparticle-on-nanocavity plasmonic modes. Ru conformally coated on the sidewalls of CNTs enables a spoof surface plasmon polariton mode for spectra selectivity; Ru nanoparticles formed at the tips of CNTs enable a localized surface plasmon resonance mode and plasmon hybridization for omnidirectional broadband solar absorption. The fabricated Ru-CNT RSSA has a total solar absorption (TSA) of 96.1% with sharp spectral cutoff at 2.21 µm. The TSA is maintained at over 90% for an incident angle of 56°. Our findings therefore guide full-spectrum optical and thermal control from visible to the far-infrared.

Limiting Mechanisms and Scaling of Electrostatically Controlled Adhesion of Soft Nanocomposite Surfaces for Robotic Gripping.

Surfaces with switchable adhesive properties are employed by robots to quickly grip and release objects and thereby to perform dexterous manipulation and locomotion tasks. Robotic grippers with switchable adhesion have been developed using structured polymers and electrostatic mechanisms. However, manipulating delicate items can be challenging as this requires strong, switchable gripping forces that do not damage the target object. Soft nanocomposite electroadhesives (SNEs) were recently introduced as an option for handling such objects. The technology integrates an electrostatic adhesion mechanism into a mechanically compliant surface formed from dielectric-coated carbon nanotubes (CNTs) to ensure soft contact with target objects. In this study we explore the scaling of the electrostatic adhesion of SNEs, toward their potential application in macroscale grasping and manipulation. We measure electroadhesive pressures on millimeter-scale areas of up to ∼20 kPa with an on/off adhesion ratio of ∼700. Based on the measured forces and simple modeling, we conclude that the maximum achievable SNE adhesion forces are determined by dielectric breakdown in the insulating coating and surrounding air. Consequently, the SNE surface behaves as a parallel capacitor plate placed at an effective distance of 2.9 µm from the target object, despite being in contact with the target and therefore having the contacting CNTs separated from the surface by ∼2 nm dielectric coating. This mechanistic understanding of soft nanocomposite electroadhesives outlines the capabilities of the technology and informs their design for advanced manufacturing applications.

Strong, Ultralight Nanofoams with Extreme Recovery and Dissipation by Manipulation of Internal Adhesive Contacts.

Advances in three-dimensional nanofabrication techniques have enabled the development of lightweight solids, such as hollow nanolattices, having record values of specific stiffness and strength, albeit at low production throughput. At the length scales of the structural elements of these solids-which are often tens of nanometers or smaller-forces required for elastic deformation can be comparable to adhesive forces, rendering the possibility to tailor bulk mechanical properties based on the relative balance of these forces. Herein, we study this interplay via the mechanics of ultralight ceramic-coated carbon nanotube (CNT) structures. We show that ceramic-CNT foams surpass other architected nanomaterials in density-normalized strength and that, when the structures are designed to minimize internal adhesive interactions between CNTs, more than 97% of the strain after compression beyond densification is recovered. Via experiments and modeling, we study the dependence of the recovery and dissipation on the coating thickness, demonstrate that internal adhesive contacts impede recovery, and identify design guidelines for ultralight materials to have maximum recovery. The combination of high recovery and dissipation in ceramic-CNT foams may be useful in structural damping and shock absorption, and the general principles could be broadly applied to both architected and stochastic nanofoams.

Nanomechanical elasticity and fracture studies of lithium phosphate (LPO) and lithium tantalate (LTO) solid-state electrolytes.

All-solid-state batteries (ASSBs) have attracted much attention due to their enhanced energy density and safety as compared to traditional liquid-based batteries. However, cyclic performance depreciates due to microcrack formation and propagation at the interface of the solid-state electrolytes (SSEs) and electrodes. Herein, we studied the elastic and fracture behavior of atomic layer deposition (ALD) synthesized glassy lithium phosphate (LPO) and lithium tantalate (LTO) thin films as promising candidates for SSEs. The mechanical behavior of ALD prepared SSE thin films with a thickness range of 5 nm to 30 nm over suspended single-layer graphene was studied using an atomic force microscope (AFM) film deflection technique. Scanning transmission electron microscopy (STEM) coupled with AFM was used for microstructural analysis. LTO films exhibited higher stiffness and higher fracture forces as compared to LPO films. Fracture in LTO films occurred directly under the indenter in a brittle fashion, while LPO films failed by a more complex fracture mechanism including significant plastic deformation prior to the onset of complete fracture. The results and methodology described in this work open a new window to identify the potential influence of SSEs mechanical performance on their operation in flexible ASSBs.

Soft nanocomposite electroadhesives for digital micro- and nanotransfer printing.

Automated handling of microscale objects is essential for manufacturing of next-generation electronic systems. Yet, mechanical pick-and-place technologies cannot manipulate smaller objects whose surface forces dominate over gravity, and emerging microtransfer printing methods require multidirectional motion, heating, and/or chemical bonding to switch adhesion. We introduce soft nanocomposite electroadhesives (SNEs), comprising sparse forests of dielectric-coated carbon nanotubes (CNTs), which have electrostatically switchable dry adhesion. SNEs exhibit 40-fold lower nominal dry adhesion than typical solids, yet their adhesion is increased >100-fold by applying 30 V to the CNTs. We characterize the scaling of adhesion with surface morphology, dielectric thickness, and applied voltage and demonstrate digital transfer printing of films of Ag nanowires, polymer and metal microparticles, and unpackaged light-emitting diodes.

Static and dynamic calibration of torsional spring constants of cantilevers.

A method for calibrating the dynamic torsional spring constant of cantilevers by directly measuring the thermally driven motion of the cantilever with an interferometer is presented. Random errors in calibration were made negligible (<1%) by averaging over multiple measurements. The errors in accuracy of ±5% or ±10% for both of the cantilevers calibrated in this study were limited only by the accuracy of the laser Doppler vibrometer (LDV) used to measure thermal fluctuations. This is a significant improvement over commonly used methods that result in large and untraceable errors resulting from assumptions made about the cantilever geometry, material properties, and/or hydrodynamic physics of the surroundings. Subsequently, the static torsional spring constant is determined from its dynamic counterpart after careful LDV measurements of the torsional mode shape, backed by finite element analysis simulations. A meticulously calibrated cantilever is used in a friction force microscopy experiment that measures the friction difference and interfacial shear strength (ISS) between graphene and a silicon dioxide AFM probe. Accurate calibration can resolve discrepancies between different experimental methods, which have contributed to a large scatter in the reported friction and ISS values in the literature to date.

Enhancement of ε-poly-L-lysine production by overexpressing the ammonium transporter gene in Streptomyces albulus PD-1.

The antibacterial polymer ɛ-poly-L-lysine (ε-PL) has been widely used as a safe food preservative. As the synthesis of ε-PL requires a rich supply of nitrogen, the efficiency of nitrogen translocation and utilization is extremely important. The objective of this study was to improve the production of ε-PL by overexpressing the ammonium transporter gene amtB in Streptomyces albulus PD-1. Using the recombinant bacteria, the optimum carbon-to-nitrogen ratio in the synthesis stage of fermentation increased from 3 to 4.71, compared with that obtained using the wild-type strain, and the utilization efficiency of ammonium was improved too. Ultimately, the production of ε-PL increased from 22.7 to 35.7 g/L upon fed-batch cultivation in a 5 L bioreactor. Determination of the expression of the genes and enzymes associated with ammonium metabolism and ε-PL synthesis revealed that the overexpression of amtB in S. albulus PD-1 enhanced ε-PL biosynthesis by increasing the activity of the corresponding metabolic pathways. To the best of our knowledge, this is the first report on enhancing ε-PL production by overexpression of the amtB gene in an ε-PL-producing strain.

Mechanical stability of the cell nucleus - roles played by the cytoskeleton in nuclear deformation and strain recovery.

Extracellular forces transmitted through the cytoskeleton can deform the cell nucleus. Large nuclear deformations increase the risk of disrupting the integrity of the nuclear envelope and causing DNA damage. The mechanical stability of the nucleus defines its capability to maintain nuclear shape by minimizing nuclear deformation and allowing strain to be minimized when deformed. Understanding the deformation and recovery behavior of the nucleus requires characterization of nuclear viscoelastic properties. Here, we quantified the decoupled viscoelastic parameters of the cell membrane, cytoskeleton, and the nucleus. The results indicate that the cytoskeleton enhances nuclear mechanical stability by lowering the effective deformability of the nucleus while maintaining nuclear sensitivity to mechanical stimuli. Additionally, the cytoskeleton decreases the strain energy release rate of the nucleus and might thus prevent shape change-induced structural damage to chromatin.

Nonlinear fracture toughness measurement and crack propagation resistance of functionalized graphene multilayers.

Despite promising applications of two-dimensional (2D) materials, one major concern is their propensity to fail in a brittle manner, which results in a low fracture toughness causing reliability issues in practical applications. We show that this limitation can be overcome by using functionalized graphene multilayers with fracture toughness (J integral) as high as ~39 J/m2, measured via a microelectromechanical systems-based in situ transmission electron microscopy technique coupled with nonlinear finite element fracture analysis. The measured fracture toughness of functionalized graphene multilayers is more than two times higher than graphene (~16 J/m2). A linear fracture analysis, similar to that previously applied to other 2D materials, was also conducted and found to be inaccurate due to the nonlinear nature of the stress-strain response of functionalized graphene multilayers. A crack arresting mechanism of functionalized graphene multilayers was experimentally observed and identified as the main contributing factor for the higher fracture toughness as compared to graphene. Molecular dynamics simulations revealed that the interactions among functionalized atoms in constituent layers and distinct fracture pathways in individual layers, due to a random distribution of functionalized carbon atoms in multilayers, restrict the growth of a preexisting crack. The results inspire potential strategies for overcoming the relatively low fracture toughness of 2D materials through chemical functionalization.

Role of graphene in enhancing the mechanical properties of TiO2/graphene heterostructures.

Graphene has been integrated in many heterogeneous structures in order to take advantage of its superior mechanical properties. However, the complex mechanical response of heterogeneous films incorporating graphene is not well understood. Here, we studied the mechanical behavior of atomic layer deposition (ALD) synthesized TiO2/graphene, as a representative building block of a typical composite, to understand the mechanical behavior of heterostructures using an experiment-computational approach. The inclusion of graphene was found to significantly enhance the Young's modulus of TiO2/graphene hetero-films for films below a critical thickness of 3 nm, beyond which the Young's modulus approaches that of pure TiO2 film. A rule-of-mixtures was found to reasonably estimate the modulus of the TiO2/graphene hetero-film. Experimentally, these hetero-films were observed to fail via brittle fracture. Complimentary density functional theory and finite element modeling demonstrates strong adhesion at the graphene TiO2 interface and that graphene serves as a reinforcement, providing the hetero-film with an ability to sustain significantly high stresses at the point of failure initiation. The results and methodology described herein can contribute to the rational design of strong and reliable ultrathin hetero-films for versatile applications.

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration.

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

In situ TEM tensile testing of carbon-linked graphene oxide nanosheets using a MEMS device.

This paper reports in situ transmission electron microscopy (TEM) tensile testing of carbon-linked graphene oxide nanosheets using a monolithic TEM compatible microelectromechanical system device. The set-up allows direct on-chip nanosheet thickness mapping, high resolution electron beam linking of a pre-fractured nanosheet, and mechanical tensile testing of the nanosheet. This technique enables simultaneous mechanical and high energy electron beam characterization of 2D nanomaterials.

Interfacial Shear Strength of Multilayer Graphene Oxide Films.

Graphene oxide (GO) is considered as one of the most promising layered materials with tunable physical properties and applicability in many important engineering applications. In this work, the interfacial behavior of multilayer GO films was directly investigated via GO-to-GO friction force microscopy, and the interfacial shear strength (ISS) was measured to be 5.3 ± 3.2 MPa. Based on high resolution atomic force microscopy images and the available chemical data, targeted molecular dynamics simulations were performed to evaluate the influence of functional structure, topological defects, and interlayer registry on the shear response of the GO films. Theoretical values for shear strength ranging from 17 to 132 MPa were predicted for the different structures studied, providing upper bounds for the ISS. Computational results also revealed the atomic origins of the stochastic nature of friction measurements. Specifically, the wide scatter in experimental measurements was attributed to variations in functional structure and topological defects within the sliding volume. The findings of this study provide important insight for understanding the significant differences in strength between monolayer and bulk graphene oxide materials and can be useful for engineering topological structures with tunable mechanical properties.

Systematic unravelling of the biosynthesis of poly (L-diaminopropionic acid) in Streptomyces albulus PD-1.

Poly(L-diaminopropionic acid) (PDAP) is one of the four homopoly(amino acid)s that have been discovered in nature. However, the molecular mechanism of PDAP biosynthesis has yet to be described. In this work, the general layout of the PDAP biosynthetic pathway is characterised in Streptomyces albulus PD-1 by genome mining, gene disruption, heterologous expression and in vitro feeding experiments. As a result, L-diaminopropionic acid (L-DAP), which is the monomer of PDAP, is shown to be jointly synthesised by two protein homologues of cysteine synthetase and ornithine cyclodeaminase. Then, L-DAP is assembled into PDAP by a novel nonribosomal peptide synthetase (NRPS) with classical adenylation and peptidyl carrier protein domains. However, instead of the traditional condensation or thioesterase domain of NRPSs, this NRPS has seven transmembrane domains surrounding three tandem soluble domains at the C-terminus. As far as we know, this novel single-module NRPS structure has only been reported in poly(ε-L-lysine) synthetase. The similar NRPS structure of PDAP synthetase and poly(ε-L-lysine) synthetase may be a common characteristic of homopoly(amino acid)s synthetases. In this case, we may discover and/or design more homopoly(amino acid)s by mining this kind of novel NRPS structure in the future.