Anomalous Size Effect of Pt Ultrathin Nanowires on Oxygen Reduction Reaction.

The classical size effect of Pt particles on oxygen reduction reaction (ORR) suggests that the activity and durability would decrease with reducing the particle size, self-limiting the effectiveness in maximizing the Pt utilization efficiency with the particle-size-reduction strategy. Herein, we discover an anomalous size effect based on Pt nanowires (NWs) with tunable diameters, where the monotonically increasing activity and durability for ORR were observed with decreasing the diameter from 2.4 to 1.1 nm. Our results reveal that the dominant role of increased compressive strain induced by decreasing the diameter of NWs in weakening the adsorption and suppressing the Pt dissolution accounts for this anomalous size effect, where the reduced low-coordinated sites on NWs, the intrinsic structural advantage, is the root. Our findings not only expand the knowledge to the classical size effect but also provide new implications to break through the size limit in the design of Pt-based ORR catalysts.

CDrift: An Algorithm to Correct Linear Drift From A Single High-Resolution STEM Image.

In this work, a new method to determine and correct the linear drift for any crystalline orientation in a single-column-resolved high-resolution scanning transmission electron microscopy (HR-STEM) image, which is based on angle measurements in the Fourier space, is presented. This proposal supposes a generalization and the improvement of a previous work that needs the presence of two symmetrical planes in the crystalline orientation to be applicable. Now, a mathematical derivation of the drift effect on two families of asymmetric planes in the reciprocal space is inferred. However, though it was not possible to find an analytical solution for all conditions, a simple formula was derived to calculate the drift effect that is exact for three specific rotation angles. Taking this into account, an iterative algorithm based on successive rotation/drift correction steps is devised to remove drift distortions in HR-STEM images. The procedure has been evaluated using a simulated micrograph of a monoclinic material in an orientation where all the reciprocal lattice vectors are different. The algorithm only needs four iterations to resolve a 15° drift angle in the image.

Effects of repeated yearly exposure to exercise-training on blood pressure and metabolic syndrome evolution.

OBJECTIVE: To study if repeated yearly training programs consolidate the transient blood pressure (BP) improvements of one exercise program into durable adaptations. METHODS: Obese middle-age individuals with metabolic syndrome (MetS) underwent high-intensity aerobic interval training during 16 weeks (November to mid-March) in 3 consecutive years [training group (TRAIN); N = 23]. Evolution of MetS components was compared with a matched-group that remained sedentary [control group (CONT); N = 26]. RESULTS: At the end of the first training program (0-4 months), TRAIN lowered systolic arterial pressure, blood glucose, waist circumference and MetS Z-score below CONT (-8.5 ±â€Š2.5 mmHg; -19.9 ±â€Š2.6 mg/dl; -3.8 ±â€Š0.1 cm and -0.3 ±â€Š0.1, respectively, all P < 0.05). With detraining (month 4-12) TRAIN adaptations relapsed to the levels of baseline (month 0) except for BP. A second exercise program (month 12-16) lowered blood glucose and waist circumference below CONT (-19.0 ±â€Š2.0 mg/dl; -4.1 ±â€Š0.1 cm). After detraining (month 16-24) BP, blood glucose and Z-score started below CONT values (-6.8 ±â€Š0.9 mmHg; -24.6 ±â€Š2.5 mg/dl and -0.4 ±â€Š0.05, respectively, all P < 0.05) and those differences enlarged with the last training program (month 24-28). Ten-year atherosclerotic cardiovascular disease risk estimation increased only in CONT (8.6 ±â€Š1.1-10.1 ±â€Š1.3%; year 2-3; P < 0.05). CONCLUSION: At least two consecutive years of 4-month aerobic interval training are required to chronically improve MetS (Z-score). The chronic effect is mediated by BP that does not fully return to pretraining values allowing a cumulative improvement. On the other hand, sedentarism in MetS patients during 3 years increases their predicted atherosclerotic diseases risk. CLINICALTRIALS. GOV IDENTIFIER: NCT03019796.

Origin of reduced magnetization and domain formation in small magnetite nanoparticles.

The structural, chemical, and magnetic properties of magnetite nanoparticles are compared. Aberration corrected scanning transmission electron microscopy reveals the prevalence of antiphase boundaries in nanoparticles that have significantly reduced magnetization, relative to the bulk. Atomistic magnetic modelling of nanoparticles with and without these defects reveals the origin of the reduced moment. Strong antiferromagnetic interactions across antiphase boundaries support multiple magnetic domains even in particles as small as 12-14 nm.

Analysis of electron beam damage of exfoliated MoS2 sheets and quantitative HAADF-STEM imaging.

In this work we examined MoS2 sheets by aberration-corrected scanning transmission electron microscopy (STEM) at three different energies: 80, 120 and 200 kV. Structural damage of the MoS2 sheets has been controlled at 80 kV according a theoretical calculation based on the inelastic scattering of the electrons involved in the interaction electron-matter. The threshold energy for the MoS2 material has been found and experimentally verified in the microscope. At energies higher than the energy threshold we show surface and edge defects produced by the electron beam irradiation. Quantitative analysis at atomic level in the images obtained at 80 kV has been performed using the experimental images and via STEM simulations using SICSTEM software to determine the exact number of MoS22 layers.

Compositional analysis with atomic column spatial resolution by 5th-order aberration-corrected scanning transmission electron microscopy.

We show in this article that it is possible to obtain elemental compositional maps and profiles with atomic-column resolution across an InxGa1-xAs multilayer structure from 5th-order aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. The compositional profiles obtained from the analysis of HAADF-STEM images describe accurately the distribution of In in the studied multilayer in good agreement with Muraki's segregation model [Muraki, K., Fukatsu, S., Shiraki, Y. & Ito, R. (1992). Surface segregation of In atoms during molecular beam epitaxy and its influence on the energy levels in InGaAs/GaAs quantums wells. Appl Phys Lett 61, 557-559].

ADART: an adaptive algebraic reconstruction algorithm for discrete tomography.

In this paper we suggest an algorithm based on the Discrete Algebraic Reconstruction Technique (DART) which is capable of computing high quality reconstructions from substantially fewer projections than required for conventional continuous tomography. Adaptive DART (ADART) goes a step further than DART on the reduction of the number of unknowns of the associated linear system achieving a significant reduction in the pixel error rate of reconstructed objects. The proposed methodology automatically adapts the border definition criterion at each iteration, resulting in a reduction of the number of pixels belonging to the border, and consequently of the number of unknowns in the general algebraic reconstruction linear system to be solved, being this reduction specially important at the final stage of the iterative process. Experimental results show that reconstruction errors are considerably reduced using ADART when compared to original DART, both in clean and noisy environments.

Calculation of integrated intensities in aberration-corrected Z-contrast images.

Inclusion of spatial incoherence has been shown to give quantitative agreement between non-aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images and theoretical simulations. Here we show that, using the same approach, a significant improvement in the correlation between calculated and experimental normalized integrated intensities is obtained in the InAsP ternary semiconductor alloy, but residual discrepancies remain. We have demonstrated, in good agreement with experimental intensities obtained in calibrated samples, that normalized integrated intensities show a low dependence on the sample thickness over a wide range of thickness values. This behaviour does not occur in conventional (non-aberration-corrected) images and constitutes a powerful tool for straightforward interpretation of high-resolution images in terms of atomic column-resolved compositional maps.

Direct observation of a surface induced disordering process in magnetic nanoparticles.

We present experimental evidence of surface induced disordering at magnetic FeCoPd nanoparticles during the L1(0)-A1 phase transition using high-resolution aberration-corrected electron microscopy and strain mapping. In situ electron diffraction studies show a narrow temperature range of fully ordered L1(0) structure. The order-disorder transition is size dependent and induces strong lattice deformation in outer part of the nanocrystals. The formation of unusually large strain of 20% is discussed in terms of core-shell structure formation with surface disordered layer and ordered core.

A method to determine the strain and nucleation sites of stacked nano-objects.

We determine the compositional distribution with atomic column resolution in a horizontal nanowire from the analysis of aberration-corrected high resolution Z-contrast images. The strain field in a layer capping the analysed nanowire is determined by anisotropic elastic theory from the resulting compositional map. The reported method allows preferential nucleation sites for epitaxial nanowires to be predicted with high spatial resolution, as required for accurate tuning of desired optical properties. The application of this method has been exemplified in this work for stacked InAs(P) horizontal nanowires grown on InP separated by 3 nm thick InP layers, but we propose it as a general method to be applied to other stacked nano-objects.

Prediction models of CO, SPM and SO(2) concentrations in the Campo de Gibraltar Region, Spain: a multiple comparison strategy.

The 'Campo de Gibraltar' region is a very industrialized area where very few air pollution studies have been carried out. Up to date, no model has been developed in order to predict air pollutant levels in the different towns spread in the region. Carbon monoxide (CO), Sulphur dioxide (SO(2)) and suspended particulate matter (SPM) series have been investigated (years 1999-2000-2001). Multilayer perceptron models (MLPs) with backpropagation learning rule have been used. A resampling strategy with two-fold crossvalidation allowed the statistical comparison of the different models considered in this study. Artificial neural networks (ANN) models were compared with Persistence and ARIMA models and also with models based on standard Multiple Linear Regression (MLR) over test sets with data that had not been used in the training stage. The models based on ANNs showed better capability of generalization than those based on MLR. The designed procedure of random resampling permits an adequate and robust multiple comparison of the tested models. Principal component analysis (PCA) is used to reduce the dimensionality of data and to transform exogenous variables into significant and independent components. Short-term predictions were better than medium-term predictions in the case of CO and SO(2) series. Conversely, medium-term predictions were better in the case of SPM concentrations. The predictions are significantly promising (e.g., d (SPM 24-ahead) = 0.906, d (CO 1-ahead) = 0.891, d (SO2 1-ahead) = 0.851).

The Peak Pairs algorithm for strain mapping from HRTEM images.

Strain mapping is defined as a numerical image-processing technique that measures the local shifts of image details around a crystal defect with respect to the ideal, defect-free, positions in the bulk. Algorithms to map elastic strains from high-resolution transmission electron microscopy (HRTEM) images may be classified into two categories: those based on the detection of peaks of intensity in real space and the Geometric Phase approach, calculated in Fourier space. In this paper, we discuss both categories and propose an alternative real space algorithm (Peak Pairs) based on the detection of pairs of intensity maxima in an affine transformed space dependent on the reference area. In spite of the fact that it is a real space approach, the Peak Pairs algorithm exhibits good behaviour at heavily distorted defect cores, e.g. interfaces and dislocations. Quantitative results are reported from experiments to determine local strain in different types of semiconductor heterostructures.

Quantitative strain mapping applied to aberration--corrected HAADF images.

A systematic distortion in high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) images, which may be caused by residual electrical interference, has been evaluated. Strain mapping, using the geometric phase methodology, has been applied to images acquired in an aberration-corrected STEM. This allows this distortion to be removed and so quantitative analysis of HAADF-STEM images was enabled. The distortion is quantified by applying this technique to structurally perfect and strain-free material. As an example, the correction is used to analyse an InAs/GaAs dot-in-quantum well heterostructure grown by molecular beam epitaxy. The result is a quantitative measure of internal strain on an atomic scale. The measured internal strain field of the heterostructure can be interpreted as being due to variations of indium concentration in the quantum dot.