Computations on Metallofullerenes Derivatized during Extraction: La@C80-C6H3Cl2 and La@C82-C6H3Cl2

Recently, an extraction of la metallofullerenes from soot using 1,2,4-trichlorobenzene has been reported for La@C₈₀ and La@C₈₂. In both cases, the cages were derivatized by the solvent (forming La@C₈₀-C₆H₃Cl₂ and La@C₈₂-C₆H₃Cl₂) and the following X-ray analysis disclosed rather unexpected cages: C₈₀(C _2v ;3) and C₈₂(C _3v ;7). In order to explain the challenging observations, a two-step computational treatment is presented. The first step deals with the high-temperature gas-phase formation of the underivatized endohedrals while the second step models the reaction with the solvent. The Gibbs free energies were evaluated for representative temperatures and the computational scheme was able to confirm high relative populations for the observed derivatized cages.     

Structural classification and similarity measurement of malware

This paper proposes a new lightweight method that utilizes the growing hierarchical self‐organizing map (GHSOM) for malware detection and structural classification. It also shows a new method for measuring the structural similarity between classes. A dynamic link library (DLL) file is an executable file used in the Windows operating system that allows applications to share codes and other resources to perform particular tasks. In this paper, we classify different malware by the data mining of the DLL files used by the malware. Since the malware families are evolving quickly, they present many new problems, such as how to link them to other existing malware families. The experiment shows that our GHSOM‐based structural classification can solve these issues and generate a malware classification tree according to the similarity of malware families. © 2014 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Cross-polarization/magic-angle spinning 13C nuclear magnetic resonance study of cellulose I-ethylenediamine complex

Complete assignments of the cross-polarization/magic-angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) spectrum of the cellulose I-ethylenediamine (EDA) complex, which is the intermediate of the reaction from cellulose I to cellulose III(I), were performed. In this paper, we used the 13C-enriched cellulose that was biosynthesized by Acetobacter xylinum ATCC10245 strain from culture medium containing D-(2-13C), D-(3-13C), or D-(5-13C)glucose as a carbon source. After conversion into cellulose I-EDA complex by sufficient EDA treatment, the CP/MAS 13C NMR spectra of the 13C-enriched cellulose I-EDA complexes were measured. As a result, 13C resonance lines of each carbon of the cellulose moiety in the complex appeared as a singlet, suggesting that all glucose residues of the complex are magnetically equivalent. The difference in chemical shifts for each carbon between cellulose I-EDA and cellulose I(alpha), I(beta), and III(I), respectively, suggests that the conformation of the cellulose chains for cellulose I-EDA differs from that for cellulose I(alpha), I(beta), and III(I). In addition, fitting analysis of the 13C spectrum of Valonia cellulose I-EDA complex revealed that the complex contains one EDA molecule per two glucose residues in the cellulose chain.     

Synthesis of colloidal polyoxazoline/silica hybrids prepared in an aqueous solution

New colloidal polymer hybrids with polyoxazolines such as poly(2-methyl-2-oxazoline) (PMeOZO) and poly(2-ethyl-2-oxazoline) (PEtOZO) were obtained in an aqueous solution as a sol-gel solvent. The polyoxazoline segment was incorporated into the siliceous particle and formed strong hydrogen bonds with silanol moieties, judging from TGA and FT-IR studies. Colloidal polymer hybrids exhibited no glass transition temperature of the polyoxazoline and showed excellent thermal stability and solvent-resistant property. Porous silica obtained by charring the colloidal polymer hybrids at 600 °C exhibited the peak at 3.5 Å. These results strongly indicate the homogeneous molecular scale dispersion of polyoxazoline in the colloidal silica gel matrix.     

Deciphering Structural Alterations Associated with Activity Reductions of Genetic Polymorphisms in Cytochrome P450 2A6 Using Molecular Dynamics Simulations

Cytochrome P450 (CYP) 2A6 is a monooxygenase involved in the metabolism of various endogenous and exogenous chemicals, such as nicotine and therapeutic drugs. The genetic polymorphisms in CYP2A6 are a cause of individual variation in smoking behavior and drug toxicities. The enzymatic activities of the allelic variants of CYP2A6 were analyzed in previous studies. However, the three-dimensional structures of the mutants were not investigated, and the mechanisms underlying activity reduction remain unknown. In this study, to investigate the structural changes involved in the reduction in enzymatic activities, we performed molecular dynamics simulations for ten allelic mutants of CYP2A6. For the calculated wild type structure, no significant structural changes were observed in comparison with the experimental structure. On the other hand, the mutations affected the interaction with heme, substrates, and the redox partner. In CYP2A6.44, a structural change in the substrate access channel was also observed. Those structural effects could explain the alteration of enzymatic activity caused by the mutations. The results of simulations provide useful information regarding the relationship between genotype and phenotype.     

Synthesis of dioctyl sulfosuccinate-doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light-responsive liquid marble stabilizer

Polypyrrole grains are synthesized by aqueous chemical oxidative polymerization using ferric chloride as an oxidant in the presence of bis(2-ethylhexyl) sulfosuccinate sodium salt as both a dopant and a hydrophobizing agent. The resulting grain products are characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilicity-hydrophobicity balance, (photo) thermal property, and electrical conductivity. Scanning electron microscopy studies indicate that the grains are aggregates of atypical primary grains with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirm that the polypyrrole is preferably doped with dioctyl sulfosuccinate compared with chloride ion, and dioctyl sulfosuccinate/chloride ion dopant ratio increases with an increase of bis(2-ethylhexyl) sulfosuccinate sodium salt concentration in the polymerization systems. The grains show near-infrared light-to-heat photothermal property, which is confirmed by thermography. The data obtained through X-ray photoelectron spectroscopy indicate the presence of dioctyl sulfosuccinate dopants on the surface of the grains, and therefore the dried polypyrrole grains show hydrophobic character. The dried grains can work as a light-responsive liquid marble (LM) stabilizer. Motions of the LM can be driven by near-infrared laser irradiation-induced Marangoni flow on planar air-water surface. The release of internal liquid can be achieved by controlled disruption of the LM via external stimulus application.     

Modeling and resonance suppression control for electro-hydrostatic actuator as a two-mass resonant system

Electro-hydrostatic actuators (EHAs) possess excellent power/weight ratio and space-saving properties. However, uncertainty exists with respect to the presence of non-linear behaviors and dynamic characteristics. Servo pumps, hydraulic motors, and oil-filled pipes can be regarded as motors, loads, and springs, respectively. Hence, EHAs can be modeled as two-mass resonant systems. In this paper, we show a parameter identification method for modeling EHAs as two-mass resonant systems. Then, in order to suppress the effect of resonance, self-resonance cancellation technique is implemented. As a result, phase delay is significantly improved in the position tracking.     

Transport Phenomena Within the Cathode for a Polymer Electrolyte Fuel Cell

A one-dimensional two-phase steady model is developed to analyze the coupled phenomena of cathode flooding and mass-transport limitation for a polymer electrolyte fuel cell. In the model, the liquid water transport in the porous electrode is driven by the capillary force based on Darcy's law, while the gas transport is driven by the concentration gradient based on Fick's law. Furthermore, the catalyst layer is treated as a separate computational domain. The capillary pressure continuity is imposed on the interface between the catalyst layer and the gas diffusion layer. Additionally, through Tafel kinetics, the mass transport and the electrochemical reaction are coupled together. The saturation jump at the interface between the gas diffusion layer and the catalyst layer is captured in the results. Meanwhile, the results further indicate that the flooding situation in the catalyst layer is much more serious than that in the gas diffusion layer. Moreover, the saturation level inside the cathode is largely related to the physical, material, and operating parameters. In order to effectively prevent flooding, one should first remove the liquid water residing inside the catalyst layer and keep the boundary value of the liquid water saturation as low as possible.     

Synthesis of ternary intercalation compounds of carbon fiber

Ternary intercalation compounds of carbon fiber (ICCF) were successfully synthesized by soaking pitch-based carbon fibers in solvents such as 1,2-dimethoxyethane (DME) or tetrahydrofuran (THF) containing dissolved alkali metals (lithium, sodium, or potassium). ICCF with stage-1 and random stage was synthesized in alkali metal–DME and potassium–THF systems using different types of carbon fibers. However, ICCF with stage-1 could not be synthesized in lithium– or sodium–THF systems using carbon fibers with a low graphitization degree. Furthermore, the influence of the graphitization degree in the synthesis of ICCF was discussed. The graphitization degree of the host carbon fiber, in addition to the dimensions and steric structure of the intercalated complex affected the formation of TICCF.     

Optical properties of epitaxial plzt thin films

In the epitaxial (Pb_1?x , La _x )(Zr_1?y , Ti _y )_1?x/4O₃ [PLZT] films, the composition dependence of the refractive index and electric-optic (EO) coefficient near the morphotropic phase boundary (MPB) composition was investigated. A (100/001)-oriented PLZT 10/65/35 epitaxial film is found to have isotropic optical properties. Highly (100/001)-oriented epitaxial PLZT films with compositions near the MPB on Nb–SrTiO₃ substrates were fabricated using a sol–gel process. The value of birefringence from 4?×?10^?3 to 5?×?10^?4 in PLZT epitaxial film was smaller than that of lithium niobate single crystal. The refractive index decreases with increasing lanthanum content. The difference in the refractive index obtained depended upon the lanthanum content up to 2%. This value is adequate for fabrication of waveguide structures. The EO coefficient of PLZT 9/65/35 thin films was 45 pm/V, which is larger than that of lithium niobate single crystal. A very small polarization dependence of the EO coefficient was also observed.