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. This method is versatile enough to be implemented in most commercially available FIB systems and MEMS 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. In particular, this investigation reveals that the mechanism of particle migration followed by coalescence is operative mainly across short distances (<0.5 nm). This work also shows that new Pt particles appear on the carbon support, as the result of Pt dissolution, followed by the formation of clusters, which grow by Ostwald ripening. This mechanism of Ostwald ripening is also responsible for changes in shape and particle growth, which later may result in coalescence.

Nanocelluloses: Production, Characterization and Market.

Nanocelluloses are a very promising material that has been widely explored for the most diverse applications. The pursuit for sustainable and environmentally friendly materials is in line with the nature of nanocelluloses and therefore they have emerged as the perfect candidate for plastics substitution, food additive, rheology controller, 3D printing of diverse structures, among many other possibilities. This derives from their interesting characteristics, such as reduced size and high specific surface area, high tensile strength, crystallinity and transparency, and from the fact that, such as cellulose, they are obtained from renewable sources, with relative ease for functionalization in order to obtain desired specificities. Thus, the industry is trying to react and effectively respond to the exponential growth of published research in the last years, and therefore new facilities (not only lab and pilot plants but already industrial sites) have been producing nanocelluloses. This new fibrous materials can be obtained from different raw-materials by different methodologies, leading to different types of nanocelluloses with, obviously, different characteristics. Nonetheless, technical and economical constraints have been addressed, such as the high energy demand or the clogging of homogenizers/microfluidizers.This chapter intends to present a review addressing the main features related to the production, characterization and market of nanocelluloses and providing additional information regarding the vast literature published in these domains.

Atomic Electrostatic Maps of Point Defects in MoS2.

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 MoS2 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. In addition, the absence of the sulfur atoms leads to an inversion in the polarity of the total charge distribution in these regions.

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. The process of Cu electrodeposition on Ru-W is of fundamental importance in order to create thin, continuous, and adherent films for advanced interconnect metallisation. This work investigates the effects of the current density and application method on the electro-crystallisation behaviour of Cu. The film structure, morphology, and chemical composition were assessed by digital microscopy, atomic force microscopy, scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The results show that it was possible to form a thin Cu film on Ru-W with interfacial continuity for current densities higher than 5 mA·cm-2; however, the substrate regions around large Cu particles remained uncovered. Pulse-reverse current application appears to be more beneficial than direct current as it decreased the average Cu particle size.

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 (VOPO4 ⋅2 H2 O) host is presented, with a special focus on primary alcohols. From methanol to 1-hexnaol, the intercalation rate peaks in 1-propanol (80 times faster than the slowest case in methanol). Similar kinetics of exfoliation are also found in these solvents without ferrocene. The correlation between intercalation and exfoliation is understood at atomic level by DFT calculations, which reveal the role of pre-intercalated solvent molecules play in intralayer interactions, interlayer expansion, and layer sliding.

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. The amorphous silica model is prepared using a simple melt-quench molecular dynamics method, while the reconstruction of the mesoporous nanoparticles is carried out using a methodology to avoid false symmetry in the final model. Simulated scanning transmission electron microscopy images are compared with experimental images, revealing the existence of structural domains, created by the misalignment of the pores to compensate the surface tension of these spherical nanoparticles.

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. The atomic structure coupled with Mn-valence and the distribution of the atomic ratio of oxygen obtained by electron energy loss spectroscopy reveals a thin, stable surface layer of Mn3O4, a subsurface region of Li1+x[Mn2]O4 with retention of bulk Li[Mn2]O4. This observation is compatible with the disproportionation reaction coupled with oxygen deficiency and a displacement of surface Li(+) from the Mn3O4 surface phase. These results provide a critical step toward understanding how Mn is lost from Li[Mn2]O4, once inside a battery.

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. We identify the shortest such sequences with lengths between 12 and 14. Only three absent sequences of length 12 exist and they consistently appear at the same location on two of the Ebola virus proteins, in all Ebola virus genomes, but nowhere in the human genome. The alignment-free method used is able to identify pathogen-specific signatures for quick and precise action against infectious agents, of which the current Ebola virus outbreak provides a compelling example.

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. As reduced baroreflex responsiveness is also associated with ageing, we investigated whether a BRS estimate <3 ms/mmHg could be the result of a process of physiological senescence as well as a sign of BRS dysfunction. This study involved 228 chronic heart failure patients and 60 age-matched controls. Our novel method combined transfer function BRS estimation and automatic clustering of BRS probability distributions, to define indicative levels of different BRS activities. The analysis produced a fit clustering (cophenetic correlation coefficient 0.9 out of 1) and identified one group of homogeneous patients (well separated from the others by 3 ms/mmHg) with an increased BRS-based mortality risk [hazard ratio (HR): 3.19 (1.73, 5.89), P<0.001]. The age-dependent BRS cut-off, estimated by 5% quantile regression of log (BRS) with age (considering the age-matched controls), provides a similar mortality value [HR: 2.44 (1.37, 4.43), P=0.003]. In conclusion, the 3 ms/mmHg cut-off identifies two large clusters of homogeneous heart failure (HF) patients, thus supporting the hypothesis of a natural cut-off in the HF population. Furthermore, age was found to have no statistical impact on risk assessment, suggesting that there is no need to establish age-based cut-offs because 3 ms/mmHg optimally identifies patients at high mortality risk.

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 0.69 eV while maintaining appreciable oscillator strength. Also, useful structure-energy relationships were derived, which allow for the development of more UVA filters based on 4-methylbenzylidene camphor.

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. However, under sunlight irradiation tautomerization occurs to the keto form, resulting in the loss of UV protection. In this study we have performed quantum chemical calculations to study the excited-state molecular structure and excitation spectra of the enol and keto tautomers of BMDBM. This knowledge is of the utmost importance as the starting point for studies aiming at the understanding of its activity when applied on human skin and also its fate once released into the aquatic environment. The efficiency of excitation transitions was rationalized based on the concept of molecular orbital superposition. The loss of UV protection was attributed to the enol → keto phototautomerism and subsequent photodegradation. Although this process is not energetically favorable in the singlet bright state, photodegradation is possible because of intersystem crossing to the first two triplet states.

Rheology of Suspensions of TEMPO-Oxidised and Cationic Cellulose Nanofibrils-The Effect of Chemical Pre-Treatment.

Cellulose nanofibrils (CNFs) are particles with a high aspect ratio. Typically, chemically pre-treated CNFs (containing anionic or cationic charged groups) consist of long fibrils (up to 2 µm) with very low thickness (less than 10 nm). Derived from their high aspect ratio, CNFs form strong hydrogels with high elasticity at low concentrations. Thus, CNF suspensions appear as an interesting rheology modifier to be applied in cosmetics, paints, foods, and as a mineral suspending agent, among other applications. The high viscosity results from the strong 3D fibril network, which is related to the good fibrillation of the material, allowing the nanofibrils to overlap. The overlap concentration (c*) was found to vary from ca. 0.13 to ca. 0.60 wt.% depending on the type and intensity of the pre-treatment applied during the preparation of the CNFs. The results confirm the higher tendency for the fibres treated with (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHPTAC) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) to form a 3D network, resulting in the lowest c*. For the TEMPO-oxidised CNF suspensions, it was also found that aggregation is improved at acidic pH conditions due to lower charge repulsion among fibrils, leading to an increase in the suspension viscosity as well as higher apparent yield stresses. TEMPO CNF suspensions with a low content of carboxylic groups tend to precipitate at moderately acidic pH values.

The breakdown of the word symmetry in the human genome.

Previous studies have suggested that Chargaff's second rule may hold for relatively long words (above 10nucleotides), but this has not been conclusively shown. In particular, the following questions remain open: Is the phenomenon of symmetry statistically significant? If so, what is the word length above which significance is lost? Can deviations in symmetry due to the finite size of the data be identified? This work addresses these questions by studying word symmetries in the human genome, chromosomes and transcriptome. To rule out finite-length effects, the results are compared with those obtained from random control sequences built to satisfy Chargaff's second parity rule. We use several techniques to evaluate the phenomenon of symmetry, including Pearson's correlation coefficient, total variational distance, a novel word symmetry distance, as well as traditional and equivalence statistical tests. We conclude that word symmetries are statistical significant in the human genome for word lengths up to 6nucleotides. For longer words, we present evidence that the phenomenon may not be as prevalent as previously thought.

Eco-Friendly Methods for Extraction and Modification of Cellulose: An Overview.

Cellulose is the most abundant renewable polymer on Earth and can be obtained from several different sources, such as trees, grass, or biomass residues. However, one of the issues is that not all the fractionation processes are eco-friendly and are essentially based on cooking the lignocellulose feedstock in a harsh chemical mixture, such as NaOH + Na2S, and water, to break loose fibers. In the last few years, new sustainable fractionation processes have been developed that enable the obtaining of cellulose fibers in a more eco-friendly way. As a raw material, cellulose's use is widely known and established in many areas. Additionally, its products/derivatives are recognized to have a far better environmental impact than fossil-based materials. Examples are textiles and packaging, where forest-based fibers may contribute to renewable and biodegradable substitutes for common synthetic materials and plastics. In this review, some of the main structural characteristics and properties of cellulose, recent green extraction methods/strategies, chemical modification, and applications of cellulose derivatives are discussed.

Impact of bacterial cellulose on the physical properties and printing quality of fine papers.

Bacterial nanocellulose (BNC), due to its inherent nanometric scale and strength properties, can be considered as a good candidate to be used in papermaking. This work explored the possibility of using it in the production of fine paper as a wet-end component and for the paper coating. Filler-containing handsheet production was performed with and without the presence of common additives typically used in the furnish of office papers. It was found that, under optimized conditions, BNC mechanically treated by high-pressure homogenization could improve all the evaluated paper properties (mechanical, optical and structural) without impairing the filler retention. However, paper strength was improved only to a small extent (increase in the tensile index of 8 % for a filler content of ca. 27.5 %). On the other hand, when used at the paper surface, remarkable improvements in the gamut area of >25 % in comparison to the base paper and of >40 % in comparison to starch-only coated papers were achieved for a formulation having 50 % BNC and 50 % of carboxymethylcellulose. Overall, the present results highlight the possibility of using BNC as a paper component, particularly when applied at the paper substrate as a coating agent aiming at improving printing quality.

Influence of dispersion of fibrillated cellulose on the reinforcement of coated papers.

The use of cellulose micro/nanofibrils (CMNFs) as reinforcement paper additive at industrial scale is delayed due to inconsistent results, suggesting a lack of proper consideration of some key parameters. The high influence of fibrillated nanocellulose dispersion has been recently identified as a key parameter for paper bulk reinforcement but it has not been studied for surface coating applications yet. This paper studies the effect of CMNF dispersion degree prior to their addition and during mixing with starch on the reinforcement of paper by coating. Results show that this effect depends on the type of CMNFs since it is related to the surface interactions. For a given formulation, a correlation is observed between the CMNF dispersion and the CMNF/starch mixing agitation with the rheology of the coating formulation which highly affects the paper properties. The optimal dispersion degree is different for each nanocellulose, but the best mechanical properties were always achieved at the lowest viscosity of the coating formulation. In general, the initial state of the nanocellulose 3D network, influences the mixing and smooth application of the coating and affects the reinforcement effect. Therefore, the CMNF industrial implementation in coating formulations will be facilitated by the on-line control of formulations prior to their surface application.

Assessing the Genotoxicity of Cellulose Nanomaterials in a Co-Culture of Human Lung Epithelial Cells and Monocyte-Derived Macrophages.

Cellulose micro/nanomaterials (CMNMs) are innovative materials with a wide spectrum of industrial and biomedical applications. Although cellulose has been recognized as a safe material, the unique properties of its nanosized forms have raised concerns about their safety for human health. Genotoxicity is an endpoint that must be assessed to ensure that no carcinogenic risks are associated with exposure to nanomaterials. In this study, we evaluated the genotoxicity of two types of cellulose micro/nanofibrils (CMF and CNF) and one sample of cellulose nanocrystals (CNC), obtained from industrial bleached Eucalyptus globulus kraft pulp. For that, we exposed co-cultures of human alveolar epithelial A549 cells and THP-1 monocyte-derived macrophages to a concentration range of each CMNM and used the micronucleus (MN) and comet assays. Our results showed that only the lowest concentrations of the CMF sample were able to induce DNA strand breaks (FPG-comet assay). However, none of the three CMNMs produced significant chromosomal alterations (MN assay). These findings, together with results from previous in vitro studies using monocultures of A549 cells, indicate that the tested CNF and CNC are not genotoxic under the conditions tested, while the CMF display a low genotoxic potential.

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. The stacks were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDX) mapping. The Cu film at the surface of the Cu/Co-W system exhibited grain growth starting at 300 °C, with the formation of abnormally large Cu grains starting at 450 °C. Sheet resistance reached a minimum value of 7.07 × 10-6 Ω/sq for the Cu/Co-W stack and 6.03 × 10-6 Ω/sq for the Cu/Ta stack, both for the samples annealed at 450 °C.

Effect of cationization pretreatment on the properties of cationic Eucalyptus micro/nanofibrillated cellulose.

Micro/nanofibrillated celluloses (M/NFCs) have attracted considerable research interest over the past few decades, with various pretreatments being used to reduce energy consumption and/or increase fibrillation. To date, few studies have considered cationization as a pretreatment for their preparation. In this work, quaternary ammonium groups were attached to cellulose fibers by a direct reaction with 2,3-epoxypropyltrimethylammonium chloride or by a two-step method (periodate oxidation + Girard's reagent T). The cationic fibers with degrees of substitution (DS) between 0.02 and 0.36, were subjected to homogenization treatment. The morphological properties, chemical composition, and rheological behavior were evaluated to assess the effect of DS and the effect of the cationization method (for samples with similar DS). The two-step cationization resulted in significant degradation of the cellulose structure, leading to the formation of short fibrils and solubilization of the material, ranging from 6% to almost complete solubilization at a DS of 0.36. Direct cationization resulted in longer fibrils with an average diameter of 1 µm, and no significant cellulose degradation was observed, leading to a more cohesive gel-like material (at 1 wt%). These observations clearly show the strong influence of the cationization method on the final properties of the cationic cellulosic materials.