Tip to substrate distances in STM imaging of biomolecules

STM images of single biomolecules adsorbed on conductive substrates do not reproduce the expected physical height, which generally appears underestimated. This may cause the tip to interfere with the soft biological sample during the imaging scans. Therefore, a key requirement to avoid invasive STM imaging is the knowledge, and the control, of the initial tip to substrate distance. This is connected to the setting of the tunnelling current and applied voltage, which define a tunnelling resistance. The height of the STM tip was measured by calibrating the tunnelling resistance, as a function of its vertical displacement until establishing a mechanical contact. At a tunnelling resistance of 4 x 10(9)Omega, distances of about 3 and 6 nm are estimated when flat Au substrates are imaged in water and in air, respectively. On such a ground, the relevance of the starting tip-substrate distance in determining a non-invasive imaging has been investigated for a plastocyanin mutant chemisorbed on Au(111) electrodes. At tunnelling distances sufficient to overcome the physical height of the imaged biomolecules, their lateral dimensions are found to be consistent with the crystallography, whereas they are significantly broadened for smaller distances.     

Optimal design and seismic performance of Multi‐Tuned Mass Damper Inerter (MTMDI) applied to adjacent high‐rise buildings

The tuned mass damper inerter (TMDI) is an enhanced variant of the tuned mass damper (TMD) that benefits from the mass‐amplification effect of the inerter. Here, a multi‐TMDI (MTMDI) system (comprising more than one TMDI) linking two adjacent high‐rise buildings is presented as an unconventional seismic protection strategy. The relative acceleration response of the adjacent structures triggers large reaction forces of the inerter devices in the MTMDI, which in turn efficiently improve the seismic performance of the two buildings. By addressing a real project of two adjacent high‐rise buildings connected by two corridors equipped with the proposed MTMDI system, the displacement‐, interstory drift‐, and acceleration‐based parametric optimizations are separately performed by employing Nondominated Sorting Genetic Algorithm II (NSGA‐II) under 44 ground motions from the FEMA P695 far‐field record set. It is found that the frequency content of the seismic input has strong impact on the MTMDI mitigation performance. Adopting realistic mass ratio constraints, the optimally designed MTMDI outperforms both conventional MTMD and single TMDI in acceleration control, while it is not much effective in mitigating the displacement response due to the highly flexible nature of the high‐rise buildings, in contrast to other literature studies generally focused on low‐to‐medium rise buildings.     

Acute poisoning with pesticides in the state of Mato Grosso do Sul, Brazil

Exposure to pesticides has been the source of many acute and chronic health problems in the rural population, mainly in developing countries. The objective of this study was to characterize the poisonings from acute exposure to agricultural pesticides used in the state of Mato Grosso do Sul, Brazil, from 1992 to 2002, which were reported to the Integrated Center of Toxicological Vigilance of the State Health Department. A total of 1355 involuntary (accidental or occupational) and voluntary (intentional self-poisoning) cases were reported during the period of the study. The majority of the poisonings occurred with men ranging in age from 15 to 49 years of age (55.1%). One hundred seventy-six poisonings lead to death, with a case fatality rate (CFR) three times higher than the average Brazilian CFR. The pesticide poisoning rates, per 100,000 inhabitants living in rural areas, ranged from 25 to 65.7 during the period of the study. In 2000, the micro-region of Campo Grande, where the state capital is located, had the highest rate, with 100.5 exposure/100,000 inhabitants, followed by Dourados, the larger agricultural region of the state. Insecticides were involved in 75.7% of the poisoning cases, followed by herbicides, with 12.2% of the cases. The anticholinestherase insecticides methamidophos, carbofuran and monochrotophos were the primary pesticides involved in the poisonings. The insecticide dimethoate was associated with the highest CFR (30.8%). The high rates of pesticide poisoning in the rural populations of certain regions of the state of Mato Grosso do Sul indicate the need for a more detailed study concerning the risk of pesticide poisoning among these populations.     

Accuracy analysis of the amplitude estimation of a sine-wave by the energy-based method using the direct and indirect procedures

The energy-based method (EBM) can be used to estimate the amplitude of a sine-wave either directly from Discrete Fourier Transform (DFT) samples or indirectly. In this paper the accuracies achieved with both these approaches are compared when some of the most commonly used cosine class windows are adopted. The effect on the estimation accuracy of the algorithm error, the spectral interference from the image component, and wideband noise superimposed to the sine-wave signal are separately evaluated and compared. The statistical efficiencies of both procedures with respect to the unbiased single-tone Cramér-Rao lower bound are determined and compared. Moreover, the overall root mean square of the amplitude estimation error achieved when taking into account all the three contributions above is derived for both direct and indirect estimation procedures. The accuracy of the obtained expressions is verified by means of computer simulations. Besides, experimental data validate the theoretical results.     

Mixed Pro- and Anti-Oxidative Effects of Pomegranate Polyphenols in Cultured Cells

In recent years, the number of scientific papers concerning pomegranate (Punica granatum L.) and its health properties has increased greatly, and there is great potential for the use of bioactive-rich pomegranate extracts as ingredients in functional foods and nutraceuticals. To translate this potential into effective strategies it is essential to further elucidate the mechanisms of the reported bioactivity. In this study HepG2 cells were supplemented with a pomegranate fruit extract or with the corresponding amount of pure punicalagin, and then subjected to an exogenous oxidative stress. Overall, upon the oxidative stress the gene expression and activity of the main antioxidant enzymes appeared reduced in supplemented cells, which were more prone to the detrimental effects than unsupplemented ones. No differences were detected between cells supplemented with the pomegranate juice or the pure punicalagin. Although further studies are needed due to the gaps existing between in vitro and in vivo studies, our results suggest caution in the administration of high concentrations of nutraceutical molecules, particularly when they are administered in concentrated form.     

Synthesis of CeOx‐Decorated Pd/C Catalysts by Controlled Surface Reactions for Hydrogen Oxidation in Anion Exchange Membrane Fuel Cells

Due to the sluggish kinetics of the hydrogen oxidation reaction (HOR) in alkaline electrolytes, the development of more efficient HOR catalysts is essential for the next generation of anion‐exchange membrane fuel cells (AEMFCs). In this work, CeO_x is selectively deposited onto carbon‐supported Pd nanoparticles by controlled surface reactions, aiming to enhance the homogenous distribution of CeO_x and its preferential attachment to Pd nanoparticles, to achieve highly active CeO_x‐Pd/C catalysts. The catalysts are characterized by inductively coupled plasma–atomic emission spectroscopy, X‐ray diffraction, high‐resolution transmission electron microscopy, scanning transmission electron microscopy (STEM), electron energy loss spectroscopy, and X‐ray photoelectron spectroscopy to confirm the bulk composition, phases present, morphology, elemental mapping, local oxidation, and surface chemical states, respectively. The intimate contact between Pd and CeO_x is shown through high‐resolution STEM maps. The oxophilic nature of CeO_x and its effect on Pd are probed by CO stripping. The interfacial contact area between CeO_x and Pd nanoparticles is calculated for the first time and correlated to the electrochemical performance of the CeO_x‐Pd/C catalysts. Highest recorded HOR specific exchange current (51.5 mA mg^?1_Pd) and H₂–O₂ AEMFC performance (peak power density of 1,169 mW cm^?2 mg_Pd^?1) are obtained with a CeO_x‐Pd/C catalyst with Ce_0.38/Pd bulk atomic ratio.     

Power Factor Enhancement by Inhomogeneous Distribution of Dopants in Two-Phase Nanocrystalline Systems

In this work, we describe a novel idea that allows for high thermoelectric power factors in two-phase materials that are heavily doped with an inhomogeneous distribution of dopants. We show that a concurrent increase of the electrical conductivity and Seebeck coefficient and a consequent increase of the power factor can be achieved in such systems. To explain the concept, we employ a semiclassical one-dimensional model that considers both electron and phonon transport through a series connection of two-phases of the material. We discuss microscopic characteristics of the material and the formation of the two phases (grains and grain boundaries in our case) by the inhomogeneous distribution of dopants in the polycrystalline material. Our theoretical investigation reveals that: (1) the improvement in the Seebeck coefficient can be attributed to carrier filtering due to the energy barriers at the grain boundaries, and to the difference in the lattice thermal conductivity of the grains and grain boundaries, and (2) the improvement in the electrical conductivity is a result of a high Fermi level in the grains. This allows high energy carriers to contribute to transport, which increases the impurity scattering limited mean-free-path, and increases the conductivity in the grains and thus in the whole material. Such an unexpected concurrent increase of the electrical conductivity and the Seebeck coefficient was recently observed in heavily boron-doped polycrystalline silicon of grain sizes <100 nm in which a silicon-boride phase is formed around the grain boundaries. We provide a simple 1D model that explains the behavior of this system, indicating processes that can take place in heavily doped nanocrystalline materials.     

Scalable Oxygen‐Ion Transport Kinetics in Metal‐Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films

In this paper, we focus on the effect of processing‐dependent lattice strain on oxygen ion conductivity in ceria based solid electrolyte thin films. This is of importance for technological applications, such as micro‐SOFCs, microbatteries, and resistive RAM memories. The oxygen ion conductivity can be significantly modified by control of lattice strain, to an extent comparable to the effect of doping bulk ceria with cations of different diameters. The interplay of dopant radii, lattice strain, microstrain, anion‐cation near order and oxygen ion transport is analyzed experimentally and interpreted with computational results. Key findings include that films annealed at 600 °C exhibit lattice parameters close to those of their bulk counterparts. With increasing anneal temperature, however, the films exhibited substantial compaction with lattice parameters decreasing by as much as nearly 2% (viz, Δd_{600–1100 °C}: –1.7% (Sc⁺³) > –1.5% (Gd⁺³) > –1.2% (La⁺³)) for the annealing temperature range of 600–1100 °C. Remarkably 2/3^rd of the lattice parameter change obtained in bulk ceria upon changing the acceptor diameter from the smaller Sc to larger La, can be reproduced by post annealing a film with fixed dopant diameter. While the impact of lattice compaction on defect association/ordering cannot be entirely excluded, DFT computation revealed that the main effect appears to result in an increase in migration energy and consequent drop in ionic conductivity. As a consequence, it is clear that annealing procedures should be held to a minimum to maintain the optimum level of oxygen ion conductivity for energy‐related applications. Results reveal also the importance to understand the role of electro‐chemo‐mechanical coupling that is active in thin film materials.     

Synthesis,Electronic Structure,and Charge Transport Characteristics of Naphthalenediimide‐Based Co‐Polymers with Different Oligothiophene Donor Units

Naphthalenediimide (NDI)‐based polymers co‐polymerized with thienyl units are an interesting class of polymer semiconductors because of their good electron mobilities and unique film microstructure. Despite these properties, understanding how the extension of the thienyl co‐monomer affects charge transport properties remains unclear. With this goal in mind, we have synthesized a series of NDI derivatives of the parent poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)), which exhibited excellent electron mobility. The strategy comprises both the extension of the donor o‐conjugation length and the heteroatomic fusion of the thiophene rings. These newly synthesized compounds are characterized experimentally and theoretically vis‐à‐vis with P(NDI2OD‐T2) as the reference. UV‐vis data and cyclic‐voltammetry are adopted to assess the effect of the donor modification on the frontier energy levels and on the bandgap. Intra‐molecular polaronic effects are accounted for by computing the internal reorganization energy with density functional theory (DFT) calculations. Finally electrons and holes transport is experimentally investigated in field‐effect transistors (FETs), by measuring current‐voltage characteristics at variable temperatures. Overall we have identified a regime where inter‐molecular effects, such as the wavefunction overlap and the degree of energetic disorder, induced by the different donor group prevail over polaronic effects and are the leading factors in determining electrons mobility.