Nanocompression of 20 nm Silver Nanoparticles: In situ Aberration-Corrected TEM and Atomistic Simulations.

Single-crystalline nanoparticles play an increasingly important role in a wide variety of fields including pharmaceuticals, advanced materials, catalysts for fuel cells, energy materials, as well as environmental detection and monitoring. Yet, the deformation mechanisms of very small nanoparticles are still poorly understood, in particular the role played by single dislocations and their interaction with surfaces. In this work, silver nanoparticles with particularly small dimensions (≈20 nanometers in diameter) are compressed in situ in an aberration-corrected transmission electron microscopy (TEM) and molecular dynamics (MD) simulations.

Novel Method for the Preparation of Lamellas From Porous and Brittle Materials for In Situ TEM Heating/Biasing.

A novel method for the preparation of lamellas made from porous and brittle compressed green powder using a focused ion beam (FIB) is described. One of the main purposes for the development of this methodology is to use this type of samples in micro-electromechanical systems (MEMS) chips for in situ transmission electron microscopy heating/biasing experiments, concomitant with maintaining the mechanical integrity and the absence of contamination of samples. This is accomplished through a modification of the standard FIB procedure for the preparation of lamellas, the adaptation of conventional chips, as well as the specific transfer of the lamella onto the chips.

Understanding the Degradation Mechanisms of Pt Electrocatalysts in PEMFCs by Combining 2D and 3D Identical Location TEM.

The evolution of Pt nanoparticles in proton-exchanged membrane fuel cells is monitored before and after electrochemical potential cycling, using 2D and 3D identical location aberration-corrected transmission electron microscopy. This work demonstrates that 2D images might be a challenge to interpret due to the 3D nature of the carbon support. Thus, it is critical to combine both 2D and 3D observations to be able to fully understand the mechanisms associated with the durability of Pt catalyst nanoparticles.

The Effect of Ultrasonic Agitation on the Seedless Growth of Cu on Ru-W Thin Films.

Ru attracted considerable attention as a candidate to replace TaN as a diffusion barrier layer for Cu interconnect metallisation. The addition of W improves the diffusion barrier properties of Ru but appears to weaken the adhesion strength between the barrier and Cu and the direct (seedless) electroplatability behaviour. Although Cu can be directly electroplated on near equimolar Ru-W thin films, no complete substrate coverage is obtained.

Co-W Barrier Layers for Metallization of Copper Interconnects: Thermal Performance Analysis.

The back-end-of-line (BEOL) copper interconnect structure has been subjected to downscaling for the last two decades, while the materials used for conforming and assuring its physical integrity during processing have faced significant obstacles as the single-digit nanometer process node is implemented. In particular, the diffusion barrier layer system comprised of Ta/TaN has faced major constraints when it comes to the electrical performance of the smaller Cu lines, and thus alternative formulations have been investigated in recent years, such as Ru-Ta or Co-W alloys. In this work, we assess how PVD (physical vapor deposition) deposited equimolar Co-W films perform when exposed to different vacuum annealing temperatures and how these films compare with the Ta adhesion layer used for Cu seeding in terms of dewetting resistance.

Seedless Cu Electroplating on Ru-W Thin Films for Metallisation of Advanced Interconnects.

For decades, Ta/TaN has been the industry standard for a diffusion barrier against Cu in interconnect metallisation. The continuous miniaturisation of transistors and interconnects into the nanoscale are pushing conventional materials to their physical limits and creating the need to replace them. Binary metallic systems, such as Ru-W, have attracted considerable attention as possible replacements due to a combination of electrical and diffusion barrier properties and the capability of direct Cu electroplating.

Atomic Electrostatic Maps of Point Defects in MoS.

In this study, we use differential phase contrast images obtained by scanning transmission electron microscopy combined with computer simulations to map the atomic electrostatic fields of MoS monolayers and investigate the effect of sulfur monovacancies and divancancies on the atomic electric field and total charge distribution. A significant redistribution of the electric field in the regions containing defects is observed, with a progressive decrease in the strength of the projected electric field for each sulfur atom removed from its position. The electric field strength at the sulfur monovacancy sites is reduced by approximately 50% and nearly vanishes at the divacancy sites, where it drops to around 15% of the original value, demonstrating the tendency of these defects to attract positively charged ions or particles.

Seedless Cu Electroplating on Co-W Thin Films in Low pH Electrolyte: Early Stages of Formation.

The use of Ta/TaN barrier bilayer systems in electronic applications has been ubiquitous over the last decade. Alternative materials such as Co-W or Ru-W alloys have gathered interest as possible replacements due to their conjugation of favourable electrical properties and barrier layer efficiency at reduced thicknesses while enabling seedless Cu electroplating. The microstructure, morphology, and electrical properties of Cu films directly electrodeposited onto Co-W or Ru-W are important to assess, concomitant with their ability to withstand the electroplating baths/conditions.

Hybrid Organic-Inorganic Gel Electrocatalyst for Stable Acidic Water Oxidation.

Water oxidation catalysts (WOCs) are essential to electrochemical hydrogen production, but (electro)chemical instability remains a critical issue for WOCs especially under acidic conditions. Here we present a hybrid organic-inorganic polymeric dual network gel (DN gel) electrocatalyst based on earth-abundant elements oxidative polymerization of polypyrrole and simultaneous cyano-polymerization for efficient acidic water oxidation. X-ray absorption and X-ray photoelectron spectra reveal a synergistic interplay between the inorganic polymer and the organic conductive polymer in producing a favorable local coordination environment, further supported by the DFT calculation.

Silica nanocarriers with user-defined precise diameters by controlled template self-assembly.

Mesoporous silica nanoparticles (MSNs) feature ideal structural properties and surface chemistry for use as nanocarriers of molecules, polymers and biomolecules in cutting-edge applications. One important challenge remaining in their preparation is the ability to tune their diameter in the range of a few tens of nanometers, with narrow size dispersity, preferably using a simple, sustainable and scalable synthetic process. This work presents a fully controllable low-temperature and purely aqueous sol-gel method to prepare MSNs with user-defined diameters from 15 nm to 80 nm and narrow size dispersity.

Ultrafast Intercalation Enabled by Strong Solvent-Host Interactions: Understanding Solvent Effect at the Atomic Level.

Solvents play an essential role in many areas of chemistry and is the cornerstone of understanding reactivity in solution-phase reactions. Solvent effects have been widely observed in intercalation reactions; however, understanding of the influence of solvents on the thermodynamics and kinetics remains largely elusive in intercalation chemistry. Now, the solvent-dependent kinetics of ferrocene intercalation into a layered vanadyl phosphate (VOPO ⋅2 H O) host is presented, with a special focus on primary alcohols.

On the Structure of Amorphous Mesoporous Silica Nanoparticles by Aberration-Corrected STEM.

Mesoporous silica materials have demonstrated a vast spectrum of applications, stimulating an intensive field of study due to their potential use as nanocarriers. Nonetheless, when produced at the nanoscale, their structural characterization is hindered due to the re-arrangement of the pores. To address this issue, this work combines molecular dynamics simulations with electron microscopy computer simulations and experimental results to provide an insight into the structure of amorphous mesoporous silica nanoparticles.

Structural Transformation of Biochar Black Carbon by C Superstructure: Environmental Implications.

Pyrogenic carbon is widespread in soil due to wildfires, soot deposition, and intentional amendment of pyrolyzed waste biomass (biochar). Interactions between engineered carbon nanoparticles and natural pyrogenic carbon (char) are unknown. This study first employed transmission electron microscopy (TEM) and X-ray diffraction (XRD) to interpret the superstructure composing aqueous fullerene C nanoparticles prepared by prolonged stirring of commercial fullerite in water (nC-stir).

Surface Interactions between Gold Nanoparticles and Biochar.

Engineered nanomaterials are directly applied to the agricultural soils as a part of pesticide/fertilize formulations or sludge/manure amendments. No prior reports are available to understand the surface interactions between gold nanoparticles (nAu) and soil components, including the charcoal black carbon (biochar). Retention of citrate-capped nAu on 300-700 °C pecan shell biochars occurred rapidly and irreversibly even at neutral pH where retention was less favorable.

Different hydroxyapatite magnetic nanoparticles for medical imaging: Its effects on hemostatic, hemolytic activity and cellular cytotoxicity.

Magnetic nanoparticles (MNPs) should be highly biocompatible, stable and safely eliminated from the body, and can therefore be successfully used in modern medicine. Synthetic hydroxyapatite (HAP) has well established biocompatible and non-inflammatory properties, as well as a highly stable and flexible structure that allows for an easy incorporation of magnetic ions. This study characterized and compared the in vitro cytotoxicity and hemocompatibility of hydroxyapatite MNPs doped with different ions (Gd(3+/)Fe(2+)/Fe(3+)/Co(2+)).

Revealing the Reconstructed Surface of Li[Mn2]O4.

The spinel Li[Mn2]O4 is a candidate cathode for a Li-ion battery, but its capacity fades over a charge/discharge cycle of Li1-x[Mn2]O4 (0 < x < 1) that is associated with a loss of Mn to the organic-liquid electrolyte. It is known that the disproportionation reaction 2Mn(3+) = Mn(2+) + Mn(4+) occurs at the surface of a Mn spinel, and it is important to understand the atomic structure and composition of the surface of Li[Mn2]O4 in order to understand how Mn loss occurs. We report a study of the surface reconstruction of Li[Mn2]O4 by aberration-corrected scanning transmission electron microscopy.

Spontaneous baroreceptor reflex sensitivity for risk stratification of heart failure patients: optimal cut-off and age effects.

Baroreceptor reflex sensitivity (BRS) is an important prognostic factor because a reduced BRS has been associated with an adverse cardiovascular outcome. The threshold for a 'reduced' BRS was established by the ATRAMI study at BRS <3 ms/mmHg in patients with a previous myocardial infarction, and has been shown to improve risk assessment in many other cardiac dysfunctions. The successful application of this cut-off to other populations suggests that it may reflect an inherent property of baroreflex functioning, so our goal is to investigate whether it represents a 'natural' partition of BRS values.

An alignment-free method to find and visualise rearrangements between pairs of DNA sequences.

Species evolution is indirectly registered in their genomic structure. The emergence and advances in sequencing technology provided a way to access genome information, namely to identify and study evolutionary macro-events, as well as chromosome alterations for clinical purposes. This paper describes a completely alignment-free computational method, based on a blind unsupervised approach, to detect large-scale and small-scale genomic rearrangements between pairs of DNA sequences.

Three minimal sequences found in Ebola virus genomes and absent from human DNA.

Motivation: Ebola virus causes high mortality hemorrhagic fevers, with more than 25 000 cases and 10 000 deaths in the current outbreak. Only experimental therapies are available, thus, novel diagnosis tools and druggable targets are needed.

Results: Analysis of Ebola virus genomes from the current outbreak reveals the presence of short DNA sequences that appear nowhere in the human genome.

On the morphology of cellulose nanofibrils obtained by TEMPO-mediated oxidation and mechanical treatment.

The morphological properties of cellulose nanofibrils obtained from eucalyptus pulp fibres were assessed. Two samples were produced with the same chemical treatment (NaClO/NaBr/TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) oxidation), but distinct mechanical treatment intensities during homogenization. It was shown that the nanofibrils production yield increases with the mechanical energy.

A theoretical study of the UV absorption of 4-methylbenzylidene camphor: from the UVB to the UVA region.

In this study, a theoretical approach was used to study the UV absorption of the UVB filter, 4-methylbenzylidene camphor. The main objective of this work was to design new UVA filters based on this rather photo-stable compound, so that photo-degradation in this UV region can be avoided without the use of other molecules. This objective was achieved by the simultaneous addition of two appropriate substituents, which led to red-shifts of up to 0.

Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.

Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction.

Structural, energetic, and UV-Vis spectral analysis of UVA filter 4-tert-butyl-4'-methoxydibenzoylmethane.

The growing awareness of the harmful effects of ultraviolet (UV) solar radiation has increased the production and consumption of sunscreen products, which contain organic and inorganic molecules named UV filters that absorb, reflect, or scatter UV radiation, thus minimizing negative human health effects. 4-tert-Butyl-4'-methoxydibenzoylmethane (BMDBM) is one of the few organic UVA filters and the most commonly used. BMDBM exists in sunscreens in the enol form which absorbs strongly in the UVA range.

DNA sequences at a glance.

Data summarization and triage is one of the current top challenges in visual analytics. The goal is to let users visually inspect large data sets and examine or request data with particular characteristics. The need for summarization and visual analytics is also felt when dealing with digital representations of DNA sequences.

In situ transmission electron microscopy observations of sublimation in silver nanoparticles.

In situ heating experiments were performed in a transmission electron microscope (TEM) to monitor the thermal stability of silver nanoparticles. The sublimation kinetics from isothermal experiments on individual nanoparticles was used to assess the actual temperatures of the nanoparticles by considering the localized heating from the electron beam. For isolated nanoparticles, beam heating under normal TEM operating conditions was found to increase the temperature by tens of degrees.