Concepts for chemical state analysis at constant probing depth by lab-based XPS/HAXPES combining soft and hard X-ray sources

The greater information depth provided in hard X-ray photoelectron spectroscopy (HAXPES) enables nondestructive analyses of the chemistry and electronic structure of buried interfaces. Moreover, for industrially relevant elements like Al, Si, and Ti, the combined access to the Al 1s, Si 1s, or Ti 1s photoelectron line and its associated Al KLL, Si KLL, or Ti KLL Auger transition, as required for local chemical state analysis on the basis of the Auger parameter, is only possible with hard X-rays. Until now, such photoemission studies were only possible at synchrotron facilities. Recently, however, the first commercial XPS/HAXPES systems, equipped with both soft and hard X-ray sources, have entered the market, providing unique opportunities for monitoring the local chemical state of all constituent ions in functional oxides at different probing depths, in a routine laboratory environment. Bulk-sensitive shallow core levels can be excited using either the hard or soft X-ray source, whereas more surface-sensitive deep core-level photoelectron lines and associated Auger transitions can be measured using the hard X-ray source. As demonstrated for thin Al₂O₃, SiO₂, and TiO₂ films, the local chemical state of the constituting ions in the oxide may even be probed at near-constant probing depth by careful selection of sets of photoelectron and Auger lines, as excited with the combined soft and hard X-ray sources. We highlight the potential of lab-based HAXPES for the research on functional oxides and also discuss relevant technical details regarding the calibration of the kinetic binding energy scale.     

Three-dimensional printing of conducting polymer microstructures into transparent polymer sheet: Relationship between process resolution and illumination conditions

Three-dimensional (3D) polypyrrole microstructures were successfully obtained in a transparent polymer sheet by 3D scanning of the laser focal point. The lateral process resolution of the microstructures was studied under different photofabrication conditions such as the repetition rate of the femtosecond pulse laser and the waiting time of the laser focal point scanning. As a result, a very small line width of the polypyrrole deposition of less than 500 nm was realized with good reproducibility.     

Both electron and hole Dirac cone states in Ba(FeAs)2 confirmed by magnetoresistance

Quantum transport of Dirac cone states in the iron pnictide Ba(FeAs)(2) with a d-multiband system is studied by using single crystal samples. Transverse magnetoresistance develops linearly against the magnetic field at low temperatures. The transport phenomena are interpreted in terms of the zeroth Landau level by applying the theory predicted by Abrikosov. The results of the semiclassical analyses of a two carrier system in a low magnetic field limit show that both the electron and hole reside as the high mobility states. Our results show that pairs of electron and hole Dirac cone states must be taken into account for an accurate interpretation in iron pnictides, which is in contrast with previous studies.     

Space-selective modification of the magnetic properties of transparent Fe3+-doped glass by femtosecond-laser irradiation

We have demonstrated spatially selective modification of the magnetic properties of transparent iron-oxide-doped glass by femtosecond- (fs-) laser irradiation and subsequent annealing. A near-infrared fs-laser beam with a wavelength of 775 nm was focused 1 mm below the surfaces of glass samples. This produces absorption peaks due to the formation of hole-trap centers in the irradiated region. Transparency was recovered after annealing at 450°C. A ferrimagnetic component was observed in the M–H curve even at room temperature, whereas the diamagnetic component dominated in the M–H curve of the as-prepared glass sample. This indicates that fs-laser irradiation enhanced the magnetization in the irradiated area. The irradiated and annealed glass sample also exhibited superparamagnetic blocking in the temperature dependence of the magnetization with a blocking temperature higher than room temperature. This change in magnetism is presumably due to local crystallization of ferrimagnetic nanoparticles, such as magnetite, induced by fs-laser irradiation and annealing. The magnetic and optical properties of glass that had been annealed but not irradiated by a fs-laser beam remained unchanged.     

A surface plasmon resonance sensor on a compact disk-type microfluidic device

A surface plasmon resonance (SPR) sensor on a compact disk (CD)-type microfluidic device was developed to miniaturize the elements of a complete analytical system, pump and valves. The CD-type microfluidic device was fabricated by attaching a polydimethylsiloxane disk plate that contained microchannels and reservoirs to a flat polycarbonate disk plate that contained grating films with a thin layer of Au. The optical system of the SPR sensor and the theory for its operation are based on the principle of a grating coupled-type SPR. The sample and reagent solutions in the reservoirs on the CD-type microfluidic device were sequentially introduced into the detection chamber by centrifugal force generated by the rotation of the microfluidic device. The variation of resonance wavelength was dependent on the refractive index of the sample solution. This CD-type SPR sensor was successfully used in an immunoassay of immunoglobulin A (IgA). The anti-IgA, blocking reagent, sample and washing solution in the reservoirs were sequentially introduced into the detection chamber by changing the frequency of rotation of the microfluidic device. IgA in the sample solution was adsorbed to the anti-IgA immobilized on the Au thin layer in the detection chamber and was then detected by the SPR sensor.     

Higher-order correlated calculations based on fragment molecular orbital scheme

We have developed a new module for higher-order correlated methods up to coupled-cluster singles and doubles with perturbative triples (CCSD(T)). The matrix-matrix operations through the DGEMM routine were pursued for a number of contractions. This code was then incorporated into the ABINIT-MPX program for the fragment molecular orbital (FMO) calculations. Intra-fragment processings were parallelized with OpenMP in a node-wise fashion, whereas the message passing interface (MPI) was used for the fragment-wise parallelization over nodes. Our new implementation made the FMO-based higher-order calculations applicable to realistic proteins. We have performed several benchmark tests on the Earth Simulator (ES2), a massively parallel computer. For example, the FMO-CCSD(T)/6-31G job for the HIV-1 protease (198 amino acid residues)?Clopinavir complex was completed in 9.8?h with 512 processors (or 64 nodes). Another example was the influenza neuraminidase (386 residues) with oseltamivir calculated at the full fourth-order M?ller?CPlesset perturbation level (MP4), of which job timing was 10.3?h with 1024 processors. The applicability of the methods to commodity cluster computers was tested as well.     

3D microfluidic chips with integrated functional microelements fabricated by a femtosecond laser for studying the gliding mechanism of cyanobacteria

Phormidium, a genus of filamentous cyanobacteria, forms endosymbiotic associations with seedling roots that accelerate the growth of the vegetable seedlings. Understanding the gliding mechanism of Phormidium will facilitate improved formation of this association and increased vegetable production. To observe the gliding movements, we fabricated various microfluidic chips termed nanoaquariums using a femtosecond (fs) laser. Direct fs laser writing, followed by annealing and successive wet etching in dilute hydrofluoric acid solution, can easily produce three-dimensional (3D) microfluidics with different structures embedded in a photostructurable glass. Using the fs laser, optical waveguides and filters were integrated with the microfluidic structures in the microchips, allowing the gliding mechanism to be more easily clarified. Using this apparatus, we found that CO(2) secreted from the seedling root attracts Phormidium in the presence of light, and determined the light intensity and specific wavelength necessary for gliding.     

Hybrid femtosecond laser microfabrication to achieve true 3D glass/polymer composite biochips with multiscale features and high performance: the concept of ship‐in‐a‐bottle biochip

True three‐dimensionally (3D) integrated biochips are crucial for realizing high performance biochemical analysis and cell engineering, which remain ultimate challenges. In this paper, a new method termed hybrid femtosecond laser microfabrication which consists of successive subtractive (femtosecond laser‐assisted wet etching of glass) and additive (two‐photon polymerization of polymer) 3D microprocessing was proposed for realizing 3D “ship‐in‐a‐bottle” microchip. Such novel microchips were fabricated by integrating various 3D polymer micro/nanostructures into flexible 3D glass microfluidic channels. The high quality of microchips was ensured by quantitatively investigating the experimental processes containing “line‐to‐line” scanning mode, improved annealing temperature (645°C), increased prebaking time (18 h for 1mm‐length channel), optimal laser power (1.9 times larger than that on the surface) and longer developing time (6 times larger). The ship‐in‐a‐bottle biochips show high capabilities to provide simultaneous filtering and mixing with 87% efficiency in a shorter distance and on‐chip synthesis of ZnO microflower particles.     

Whole-body counter surveys of Miharu-town school children for four consecutive years after the Fukushima NPP accident

Comprehensive whole-body counter surveys of Miharu-town school children have been conducted for four consecutive years, in 2011–2014. This represents the only long-term sampling-bias-free study of its type conducted after the Fukushima Dai-ichi accident. For the first time in 2014, a new device called the Babyscan, which has a low ^134/137Cs MDA of <50 Bq/body, was used to screen the children shorter than 130 cm. No child in this group was found to have detectable level of radiocesium. Using the MDAs, upper limits of daily intake of radiocesium were estimated for each child. For those screened with the Babyscan, the upper intake limits were found to be ≲1 Bq/day for ¹³⁷Cs. Analysis of a questionnaire filled out by the children’s parents regarding their food and water consumption shows that the majority of Miharu children regularly consume local and/or home-grown rice and vegetables. This however does not increase the body burden.     

Enzymatic Syntheses of N-Acetyllactosamine and N-Acetylallolactosamine by the Use of β-D-Galactosidases

Abstract

A β-D-galactosidase from Bacillus circulans induced β-D-galactopyranosyl transfer from lactose predominantly to a secondary (OH-4) rather than the primary hydroxyl group (OH-6) of 2-acetamido-2-deoxy-D-glucopyranose. 4-O-β-D-Galacto-pyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-lactosamine) was thus readily synthesized on a gram scale and conveniently isolated by chromatography on a column of charcoal-Celite. On the other hand, the glycosyl transfer to the 6-position predominantly was efficiently induced to give 6-O-β-D-galactopyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-allolactosamine) by consecutive use of β-D-galactosidases from Kluyveromyces lactis and B. circulans. These enzyme reactions were efficient enough to allow the one-pot preparation of the desired disaccharides.