High-Density Frenkel Defects as Origin of N-Type Thermoelectric Performance and Low Thermal Conductivity in Mg3Sb2-Based Materials

Mg₃Sb₂-based intermetallic compounds with exceptionally high thermoelectric performance exhibit unconventional n-type dopability and anomalously low thermal conductivity, attracting much attention to the underlying mechanisms. To date, investigations have been limited to first-principle calculations and thermodynamic analysis of defect formation, and detailed experimental analysis on crystal structure and phonon modes has not been achieved. Here, a synchrotron X-ray diffraction study clarifies that, against a previous view of a simple crystal structure with a small unit cell, Mg₃Sb₂ is inherently a heavily disordered material with Frenkel defects, charge-neutral defect complexes of cation vacancies and interstitials. Ionic charge neutrality preserved in Mg₃Sb₂ is responsible for exotic n-type dopability, which is unachievable for other Zintl phase materials. The thermal conductivity of Mg₃Sb₂ exhibits deviation from the standard T⁻¹ temperature dependency with strongly limited phonon transport due to a strain field. Inelastic X-ray scattering measurement reveals enhanced phonon scattering induced by disorder. The results will draw renewed attention to crystal defects and disorder as means to explore new high-performance thermoelectric materials.     

Colossal Barocaloric Effect by Large Latent Heat Produced by First-Order Intersite-Charge-Transfer Transition

Materials which show novel thermal properties can be used to make highly efficient and environmentally friendly energy systems for thermal energy storage and refrigeration through caloric effects. An A-site-ordered quadruple perovskite-structure oxide, NdCu₃Fe₄O₁₂, is found to release significant latent heat, 25.5 kJ kg⁻¹ (157 J cc⁻¹), at the intersite-charge-transfer transition temperature near room temperature. The transition is first-order and accompanied by an unusual magnetic ordering and a large negative-thermal-expansion-like volume change, and thus, it causes a large entropy change (84.2 J K⁻¹ kg⁻¹). The observed entropy change is comparable to the largest changes reported in inorganic solid materials, and more importantly, it is utilized through a colossal barocaloric effect. The adiabatic temperature change by applying 5.1 kbar pressure is estimated to reach 13.7 K, which means efficient refrigeration can be realized through this effect.     

Effect of vacuum venting and mold wettability on the replication of micro-structured surfaces

Micro injection molding enables the manufacture of micro-scale features with good accuracy at high production rates. However, the replication of complex micro and nano features is still challenging hindering the development of new functional surface topographies. The marked thermal gradient between injected polymer and mold surface and the reduced dimensions promote a rapid drop of melt temperature that causes the incomplete filling of the micro features. This study aims to investigate the combined effects of vacuum venting and mold wettability on the replication of micro-structured surfaces. A low-viscosity polystyrene and a cyclic olefin copolymer were selected and their wetting properties were evaluated. The results showed that a polymer with high wetting properties and an elevated viscosity dependence on temperature improves the replication of the micro features. Moreover, high interfacial effects can be exploited to significantly enhance the filling ratio when applying vacuum venting.

     

Experimental study of the Mode I adhesive fracture energy in DCB specimens bonded with a polyurethane adhesive

The Mode I fracture energy of a polyurethane adhesive with low Young’s modulus was investigated. Metal adherends in standardized double cantilever beam (DCB) tests are typically too stiff for soft adhesives, making it difficult to measure the fracture energy accurately. However, soft adhesives, such as a single-component polyurethane adhesive tested in this paper, are in high demand in the automobile industry. Thus, accurate measurement techniques must be established. Flexible substrates composed of spring steel were used for the DCB tests to accommodate the deformation of the adhesive layer. First, the applicability of the flexible substrates was discussed using specimens bonded with an epoxy adhesive. For soft adhesives, however, the deformation of the adhesive layer must be considered in the calculation methods of the fracture energy. Although the deformation effect on the DCB tests has been discussed with Winkler’s elastic foundation, the crack length must be measured along with the load and displacement. To overcome the difficulty of measuring the crack length, a calculation method based on Winkler’s elastic foundation was introduced applying the compliance-based beam method (CBBM). Finally, the fracture energy of the polyurethane adhesive was discussed by comparing the calculation methods with and without measuring the crack length.     

In situ bioremediation of a cis-dichloroethylene-contaminated aquifer utilizing methane-rich groundwater from an uncontaminated aquifer

At a trichloroethylene (TCE)-contaminated site in Chikura, Chiba, Japan, TCE had spread over to the first and second aquifers over years. After 8 years of pumping and treatment, finally derivative of TCE, cis-dichloroethylene (c-DCE) remained only in the second aquifer. In this study, feasibility of a low cost in situ bioremediation utilizing groundwater of the third aquifer, which contained natural dissolved methane possibly derived from natural gas field nearby, to stimulate methane-oxidizing bacteria was examined. In vitro experiment showed that a mixture of the groundwater from the second and third aquifers stimulated a growth of methane oxidizing bacteria and enhanced c-DCE degradation. The groundwater of the third aquifer was introduced into the second aquifer in situ. The population of methanotrophs with high V(max) and K(m) for methane uptake increased, resulting in successful degradation of c-DCE at a monitoring well 2m downgradient of the injection well.     

GFP expression by intracellular gene delivery of GFP-coding fragments using nanocrystal quantum dots

Gene therapy is an attractive approach to supplement a deficient gene function. Although there has been some success with specific gene delivery using various methods including viral vectors and liposomes, most of these methods have a limited efficiency or also carry a risk for oncogenesis. We herein report that quantum dots (QDs) conjugated with nuclear localizing signal peptides (NLSP) successfully introduced gene-fragments with promoter elements, which promoted the expression of the enhanced green fluorescent protein (eGFP) gene in mammalian cells. The expression of eGFP protein was observed when the QD/gene-construct was added to the culture media. The gene-expression efficiency varied depending on multiple factors around QDs, such as (1) the reading direction of the gene-fragments, (2) the quantity of gene-fragments attached on the surface of the QD-constructs, (3) the surface electronic charges varied according to the structure of the QD/gene-constructs, and (4) the particle size of QD/gene complex varied according to the structure and amounts of gene-fragments. Using this QD/gene-construct system, eGFP protein could be detected 28 days after the gene-introduction whereas the fluorescence of QDs had disappeared. This system therefore provides another method for the intracellular delivery of gene-fragments without using either viral vectors or specific liposomes.     

Calculating accumulations

Theaccumulation strategy consists of generalizing a function over an algebraic data structure by inclusion of an extra parameter, anaccumulating parameter, for reusing and propagating intermediate results. However, there remain two major difficulties in this accumulation strategy. One is to determinewhere andwhen to generalize the original function. The other, surprisingly not yet receiving its worthy consideration, is how to manipulate accumulations. To overcome these difficulties, we propose to formulate accumulations ashigher order catamorphisms, and provide several general transformation rules for calculating accumulations (i.e., finding and manipulating accumulations) bycalculation-based (rather than a search-based) program transformation methods. Some examples are given for illustration. Zhenjiang Hu, Dr.Eng.: He is an Assistant Professor in Information Engineering at the University of Tokyo. He received his BS and MS in Computer Science from Shanghai Jiao Tong University in 1988 and 1990 respectively, and his Dr. Eng. degree in Information Engineering from the University of Tokyo in 1996. His current research concerns programming languages, functional programming, program transformation, and parallel processing. Hideya Iwasaki, Dr.Eng.: He is an Associate Professor in Information Engineering at the University of Tokyo. He received the M.E. degree in 1985, the Dr. Eng. degree in 1988 from the University of Tokyo. His research interests are list processing languages, functional languages, parallel processing, and constructive algorithmics. Masato Takeichi, Dr.Eng.: He is Professor in Mathematical Engineering and Information Engineering at the University of Tokyo since 1993. After graduation from the University of Tokyo, he joined the faculty at the University of Electro-Communications in Tokyo before he went back to work at the University of Tokyo in 1987. His research concerns the design and implementation of functional programming languages, and calculational program transformation systems.     

Primary targets of fluoroquinolones in Streptococcus pneumoniae

Mutants of wild-type Streptococcus pneumoniae IID553 with mutations in parC were obtained by selection with trovafloxacin, levofloxacin, norfloxacin, and ciprofloxacin. All of the parC mutants were cross-resistant to the selecting agents but were not resistant to gatifloxacin and sparfloxacin. On the other hand, gyrA mutants were isolated by selection with gatifloxacin and sparfloxacin. The gyrA mutants were cross-resistant to gatifloxacin and sparfloxacin but were not resistant to the other fluoroquinolones tested. These results suggest that in wild-type S. pneumoniae the primary target of trovafloxacin, levofloxacin, norfloxacin, and ciprofloxacin is topoisomerase IV, whereas the primary target of gatifloxacin and sparfloxacin is DNA gyrase.     

Autotaxin May Have Lysophosphatidic Acid-Unrelated Effects on Three-Dimension (3D) Cultured Human Trabecular Meshwork (HTM) Cells

Purpose: The objective of the current study was to evaluate the effects of the autotaxin (ATX)–lysophosphatidic acid (LPA) signaling axis on the human trabecular meshwork (HTM) in two-dimensional (2D) and three-dimensional (3D) cultures of HTM cells. Methods: The effects were characterized by transendothelial electrical resistance (TEER) and FITC-dextran permeability (2D), measurements of size and stiffness (3D), and the expression of several genes, including extracellular matrix (ECM) molecules, their modulators, and endoplasmic reticulum (ER) stress-related factors. Results: A one-day exposure to 200 nM LPA induced significant down-sizing effects of the 3D HTM spheroids, and these effects were enhanced slightly on longer exposure. The TEER and FITC-dextran permeability data indicate that LPA induced an increase in the barrier function of the 2D HTM monolayers. A one-day exposure to a 2 mg/L solution of ATX also resulted in a significant decrease in the sizes of the 3D HTM spheroids, and an increase in stiffness was also observed. The gene expression of several ECMs, their regulators and ER-stress related factors by the 3D HTM spheroids were altered by both ATX and LPA, but in different manners. Conclusions: The findings presented herein suggest that ATX may have additional roles in the human TM, in addition to the ATX–LPA signaling axis.     

Preparation of oxygen gas barrier poly(ethylene terephthalate) films by deposition of silicon oxide films plasma‐polymerized from a mixture of tetramethoxysilane and oxygen

To prepare silicon oxide (SiOx)‐deposited poly(ethylene terephthalate) films with high oxygen gas barrier capability, SiOx deposition by plasma polymerization has been investigated from the viewpoint of chemical composition. Tetramethoxysilane (TMOS) is suitable as a starting material for the synthesis of the SiOx films. The SiOx deposition under self‐bias, where the etching action occurs around an electrode surface, is effective in eliminating carbonaceous compounds from the deposited SiOx films. There is no difference in the chemical composition between the SiOx films deposited under self‐bias and under no self‐bias. The SiOx films are composed of a main component of Si O Si networks and a minor component of carbonized carbons. The SiOx films deposited under no self‐bias from the TMOS/O₂ mixture show good oxygen gas barrier capability, but the SiOx films deposited under the self‐bias show poor capability. The minimum oxygen permeation rate for poly(ethylene terephthalate) films deposited SiOx film is 0.10 cm³ m⁻² day⁻¹ atm⁻¹, which corresponds to an oxygen permeability coefficient of 1.4 × 10⁻¹⁷ cm³‐cm cm⁻² s⁻¹ cm⁻¹ Hg for the SiOx film itself. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2091–2100, 1999