High transport efficiency of nanoparticles through a total-consumption sample introduction system and its beneficial application for particle size evaluation in single-particle ICP-MS.

In order to facilitate reliable and efficient determination of both the particle number concentration (PNC) and the size of nanoparticles (NPs) by single-particle ICP-MS (spICP-MS) without the need to correct for the particle transport efficiency (TE, a possible source of bias in the results), a total-consumption sample introduction system consisting of a large-bore, high-performance concentric nebulizer and a small-volume on-axis cylinder chamber was utilized. Such a system potentially permits a particle TE of 100 %, meaning that there is no need to include a particle TE correction when calculating the PNC and the NP size. When the particle TE through the sample introduction system was evaluated by comparing the frequency of sharp transient signals from the NPs in a measured NP standard of precisely known PNC to the particle frequency for a measured NP suspension, the TE for platinum NPs with a nominal diameter of 70 nm was found to be very high (i.e., 93 %), and showed satisfactory repeatability (relative standard deviation of 1.0 % for four consecutive measurements). These results indicated that employing this total consumption system allows the particle TE correction to be ignored when calculating the PNC. When the particle size was determined using a solution-standard-based calibration approach without an NP standard, the particle diameters of platinum and silver NPs with nominal diameters of 30-100 nm were found to agree well with the particle diameters determined by transmission electron microscopy, regardless of whether a correction was performed for the particle TE. Thus, applying the proposed system enables NP size to be accurately evaluated using a solution-standard-based calibration approach without the need to correct for the particle TE.

Identification of possible technical problems in determination of the major inorganic constituents of brown-rice flour by evaluating proficiency test results.

To support skill upgrading in analysis of inorganic constituents of environmental and food samples, the National Metrology Institute of Japan (NMIJ) and the National Food Research Institute (NFRI) have organized a proficiency test (PT) of determination of Mn, Fe, Cu, Zn, As, and Cd in brown-rice flour based on the international standard (ISO/IEC 17043:2010). One hundred and thirty-three sets of reports were assessed by use of the E(n)-number and z-score approaches in accordance with ISO/IEC 17043 and the international harmonized protocol for PT. The PT results and analytical procedures, reported in detail, were reviewed, and possible technical reasons for questionable or unsatisfactory results are discussed.

Baseline Assessment for the Consistency of Raman Shifts Acquired with 26 Different Raman Systems and Necessity of a Standardized Calibration Protocol.

Although Raman shifts originate from molecular vibrations and in theory must be independent of analytical systems, acquired Raman shifts, in practice, are not so. Since the consistency of Raman shifts acquired with different systems has not been investigated previously, we have compared the Raman spectra of polystyrene, benzonitrile, and cyclohexane obtained with 26 different systems. The medians of 26 measurements for the characteristic peaks were found to be 1001.3, 1001.1, and 802.0 cm-1 for polystyrene, benzonitrile, and cyclohexane, respectively, and were consistent with their corresponding ASTM E1840 values, which have been widely used for the calibration of Raman systems. However, only 16 measurements of the Raman shift of the polystyrene peak (1001.4 cm-1) met the tolerance standard of the European Pharmacopoeia (±1.5 cm-1). Thus, consistency of Raman shifts obtained using different systems is low, and this mainly originates from differences in the Raman systems rather than materials. Although correction of the offset using the Raman shift of the peaks of cyclohexane (802.0 or 2852.4 cm-1) could improve the consistency of the Raman shifts acquired with different systems, the magnitude of improvement was not uniform over the range of shift values. Thus, there is a need for a standardized calibration protocol that can be used for multiple Raman shifts of common materials to improve the consistency of Raman shifts for different systems.

Studies of CO adsorption on Pt(100), Pt(410), and Pt(110) surfaces using density functional theory.

Adsorption of CO on Pt(100), Pt(410), and Pt(110) surfaces has been investigated by density functional theory (DFT) method (periodic DMol(3)) with full geometry optimization and without symmetry restriction. Adsorption energies, structures, and vibrational frequencies of CO on these surfaces are studied by considering multiple possible adsorption sites and comparing them with the experimental data. The same site preference as inferred experiments is obtained for all the surfaces. For Pt(100), CO adsorbs at the bridge site at low coverage, but the atop site becomes most favorable for the c(2 x 2) structure at 1/2 monolayer. For Pt(410) (stepped surface with (100) terrace and (110) step), CO adsorbs preferentially at the atop site on the step edge at 1/4 monolayer, but CO populates also at other atop and bridge sites on the (100) terrace at 1/2 monolayer. The multiple possible adsorption sites probably correspond to the multiple states in the temperature-programmed desorption spectra for CO desorption. For Pt(110), CO adsorbs preferentially at the atop site on the edge for both the reconstructed (1 x 2) and the un-reconstructed (1 x 1) surfaces. When adjacent sites along the edge row begin to be occupied, the CO molecules tilt alternately by ca. 20 degrees from the surface normal in opposite directions for both the (1 x 2) and (1 x 1) surfaces.

Position-controlled marker formation by helium ion microscope for aligning a TEM tomographic tilt series.

We formed nano-dots using a helium ion microscope (HIM) equipped with a gas injection system. Because of position controllability, the nano-dot markers could be placed efficiently on a specimen using the HIM. The sizes of the dots were controlled by changing the beam radiation time. We tried for the first time to form dots on a rod-shaped specimen to use them as markers for aligning a transmission electron microscope tomographic tilt series before reconstructing 3D images.

Fabrication of marker area to align TEM tomographic tilt series of rod-shaped specimens.

In this study, we present a new method for placing markers for alignment of tomographic tilt-series of rod-shaped specimen before 3D reconstructions. By this method, markers (gold nanoparticles) were placed only on the carbon layer (referred to as the "marker area") deposited for protecting the specimen surface against ion beam irradiation; this placement was achieved by vacuum evaporation of gold with the help of a mask fabricated adjacent to the specimen. Experimental results showed that the use of the proposed method facilitates the identification of the markers in the alignment process, because the image of the marker area consists of simple high-contrast images of the gold nanoparticles on the carbon layer. The performance of the proposed method was successfully verified experimentally by applying it to a high-density Au/SiO2 nanocomposite material as a test specimen.

Calibration method of tilt and azimuth angles for alignment of TEM tomographic tilt series.

This paper describes the calibration method of the tilt and azimuth angles of specimen using a digital protractor and a laser autocollimator for alignment of electron tomography. It also suggests an easy method to check whether the specimen is tilted by 180.0°, and whether the azimuth angle is 0.0°; the method involves the use of two images of a rod-shaped specimen collected before and after a 180.0° tilt. The method is based on the assumption that these images are symmetric about the tilt axis when the azimuth angle is 0.0°. In addition, we used an experiment to demonstrate the effect of the incorrect angles on reconstructed images and simulated the image quality against distance away from tilt axis.

Automatic coarse-alignment for TEM tilt series of rod-shaped specimens collected with a full angular range.

An automatic coarse-alignment method for a tilt series of rod-shaped specimen collected with a full angular range (from alpha=-90 degrees to +90 degrees, alpha is the tilt angle of the specimen) is presented; this method is based on a cross-correlation method and uses the outline of the specimen shape. Both the rotational angle of the tilt axis and translational value of each image can be detected in the images without the use of markers. This method is performed on the basis of the assumption that the images taken at alpha=-90 degrees and alpha=+90 degrees are symmetric about the tilt axis. In this study, a carbon rod on which gold particles have been deposited is used as a test specimen for the demonstration. This method can be used as an automatic coarse-alignment method prior to the application of a highly accurate alignment method because the alignment procedure can be performed automatically except for the initial setup of some parameters.