Chemical Factors Underlying the More Rapid β-O-4 Bond Cleavage of Syringyl than Guaiacyl Lignin under Alkaline Delignification Conditions

This study aimed to clarify why the β-O-4 bond cleavage of syringyl lignin is more rapid than that of guaiacyl lignin under alkaline pulping conditions. We examined whether or not three chemical factors, acidity of the α-hydroxy group, nucleophilicity of the generated α-alkoxide, and leaving ability of the leaving phenoxide, are different between syringyl and guaiacyl lignins and control the rate of the alkaline-induced β-O-4 bond cleavage, employing dimeric non-phenolic β-O-4-type lignin model compounds (LMCs) and novel methods for estimating these three factors. The results indicated that the α-hydroxy groups of syringyl-type LMCs are relatively more acidic than those of guaiacyl-type and that syringyl nucleus is a better leaving group than guaiacyl nucleus in the β-O-4 bond cleavage. These factors result in the β-O-4 bond of syringyl lignin being more prone to the alkaline-induced cleavage than that of guaiacyl lignin.     

Stereo-Preference in the degradation of the erythro and threo isomers of β-O-4-type lignin model compounds in oxidation processes. part 2: In the reaction with hydroxyl and oxyl anion radicals under hydrogen peroxide bleaching conditions

We examined which isomer, the erythro or threo, of non-phenolic β-O-4-type lignin model compounds is stereo-preferentially attacked by hydroxyl radical and its conjugate base, oxyl anion radical, generated by the decomposition of hydrogen peroxide in the presence of ferric ion and its precipitates under hydrogen peroxide bleaching conditions. The intrinsic stereo-preference of oxyl anion radical was slightly toward the erythro isomer, while hydroxyl radical had a further smaller stereo-preference. These stereo-preferences can be explained by our prior knowledge that oxyl anion radical preferentially attacks the side-chain of the lignin model compounds rather than the aromatic nucleus. The amount of the degraded lignin model compounds became less great with decreasing pH, but reversely and intensively greater in the pH range below 10. This phenomenon can be attributed to the change in the decomposition mechanism of hydrogen peroxide accompanying the pH variation.     

Motion of Crystal Particles by the Electromagnetic Vibrations in Mg-Cu-Y Bulk Metallic Glasses

The method for producing Mg-Cu-Y and Fe-Co-B-Si-Nb bulk metallic glasses using electromagnetic vibrations is effective in forming the metallic glass phase. Disappearance or decrement of clusters by the electromagnetic vibrations applied to the liquid state is considered to cause suppression of crystal nucleation, because the electromagnetic vibrations vibrate the clusters vigorously in the melt. The purpose of this study was to investigate motion of the crystal particles by the electromagnetic vibrations in Mg-Cu-Y bulk metallic glasses. The electromagnetic vibration force vibrated the crystal particles or the clusters that become crystal nuclei in the melt, because the electric current for the electromagnetic vibrations concentrates in those. Thus, the electromagnetic vibrations were found to select vibration particles from the melt. Moreover, it was considered that composites for which second phases or other compounds are dispersed into the metallic glass phase or a nanostructure phase can be produced by the electromagnetic vibration process. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Adaptive control of maximum thermal stress in a smart piezocomposite disk

In this paper, an adaptive control problem of the maximum thermal stress in a smart composite disk is analyzed. The disk consists of a transversely isotropic structural layer onto which piezoelectric sensor and actuator layers are bonded. It is considered that an unknown heating temperature distribution acts on the structural layer and a thermally induced voltage distribution is measured on the sensor layer. The unknown heating temperature distribution is inferred from the knowledge of the measured voltage distribution. Applied voltages to electrodes arranged on every actuator layer are determined by optimization so that the maximum thermal stress in the structural layer is minimized and stress constraints imposed on the piezoelectric layers are satisfied. Finally, the suppression ratio of the maximum thermal stress is discussed based on numerical results.     

Understanding the Structural Evolution and Redox Mechanism of a NaFeO2–NaCoO2 Solid Solution for Sodium‐Ion Batteries

Na‐ion batteries have become promising candidates for large‐scale energy‐storage systems because of the abundant Na resources and they have attracted considerable academic interest because of their unique behavior, such as their electrochemical activity for the Fe³⁺/Fe⁴⁺ redox couple. The high‐rate performance derived from the low Lewis‐acidity of the Na⁺ ions is another advantage of Na‐ion batteries and has been demonstrated in NaFe_1/2Co_1/2O₂ solutions. Here, a solid solution of NaFeO₂‐NaCoO₂ is synthesized and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of operando X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and density functional theory (DFT) calculations for Na_{1– x} Fe_1/2Co_1/2O₂ reveals that the O3‐type phase transforms into a P3‐type phase coupled with Na⁺/vacancy ordering, which has not been observed in O3‐type NaFeO₂. The substitution of Co for Fe stabilizes the P3‐type phase formed by sodium extraction and could suppress the irreversible structural change that is usually observed in O3‐type NaFeO₂, resulting in a better cycle retention and higher rate performance. Although no ordering of the transition metal ions is seen in the neutron diffraction experiments, as supported by Monte‐Carlo simulations, the formation of a superlattice originating from the Na⁺/vacancy ordering is found by synchrotron X‐ray diffraction for Na_0.5Fe_1/2Co_1/2O₂, which may involve a potential step in the charge/discharge profiles.     

Single-Component Pheromone Consisting of Bombykal in a Diurnal Hawk Moth, <Emphasis Type="Italic">Neogurelca himachala sangaica</Emphasis>

Recent work has suggested that hawk moths share pheromone components but are sexually separated by qualitative and quantitative differences in their pheromone blends. During field assays on the sex pheromones of other species, a diurnal hawk moth, Neogurelca himachala sangaica (Lepidoptera: Sphingidae), was frequently captured, but the composition of the sex pheromone of this species was not known. Analysis of hexane extracts of the pheromone glands of calling female by gas chromatography (GC) using an electroantennographic detector (EAD) revealed two components that elicited EAD responses from male moth antennae. These components were identified by their mass spectra and retention indices on two GC columns as (10E,12Z)-10,12-hexadecadienal (E10,Z12–16:Ald) and a trace of its (10E,12E)-isomer (E10,E12–16:Ald) in 98:2 ratio. In field experiments, E10,Z12–16:Ald alone attracted male moths, and addition of E10,E12–16:Ald significantly reduced the attractiveness, even at the naturally-occurring ratio. Analysis of the data using a generalized linear mixed model showed that E10,Z12–16:Ald positively contributed to attractiveness, whereas E10,E12–16:Ald did so negatively, and it was concluded that the sex pheromone of N. himachala sangaica consists solely of E10,Z12–16:Ald, bombykal. The negative effect of E10,E12–16:Ald on attractiveness could promote the species-specificity of this single-component pheromone system.     

Oily Grime Formed on Hard Surfaces of Kitchen Appliances: Chemical Composition and Oxidation Mechanism

The cooking of oil-containing food products at high temperatures results in an insoluble, unsightly, greasy layer of grime on appliance surfaces in residential and commercial kitchens. Over time, adsorbed grime becomes difficult to remove using normal dishwashing detergents. A number of studies have focused on the deterioration and oxidation of oils and the harmful effects that volatile compounds associated with such processes have on human health. Little attention, however, has been paid to kitchen grime. The present study examined grime obtained from the surfaces of appliances such as sirocco fans, filters, and range hoods in residential kitchens in Tokyo. The grime was characterized by X-ray fluorescence spectroscopy (XRF), Fourier-transform infrared spectroscopy (FT-IR), size exclusion chromatography (SEC), thermal hydrolysis methylation–gas chromatography–mass spectroscopy (THM–GCMS), and nuclear magnetic resonance (NMR) techniques. The chemical composition and structure of the grime differed from those of the edible oils. The grime consisted mainly of polymerized and oxidized triacylglycerols. Bridging between unsaturated acyl groups of triglycerols occurred through thermal oxidation and aging in air, yielding their dimers, trimers, and highly polymerized products while also transforming unsaturated acyl groups into saturated ones. Cross-linking reactions involving dibasic acids also caused polymerization. Those polymerized products strongly adhered to the hard surfaces of the appliances. Small amounts of cellulose fibers from air or towel may also play a role in mechanically stabilizing the dirt structure.

Measurements of fiber bundle interfacial properties of three-dimensionally reinforced carbon/carbon composites up to 2273 K

Experimental techniques for evaluating the interfacial properties between fiber bundles and the matrix of three-dimensionally reinforced carbon/carbon composites were examined. Specially arranged fiber bundle push-out and pull-out tests were conducted up to 2273 K in vacuum. In these tests, a fiber bundle in the specimens was extruded or pulled out by external compressive or tensile loads. Post-fracture observations revealed that a shear fracture was successfully induced within the carbon matrices at the loaded fiber bundle interface. The interfacial shear strength and initial sliding stress of the fiber bundle monotonically increased with the test temperature. The relief of residual thermal stress and increases in the frictional resistance and anchor effect at the fiber bundle interface were considered to be the major mechanisms that caused the enhancements. An increase in the heat treatment temperature during the processing of the composites resulted in a significant decrease in and .     

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.     

Autonomous mobile robot based on behavior decision skill and control skill of the operator

This paper introduces a human skill base control algorithm using artificial neural networks and fuzzy reasoning for an autonomous mobile robot. Neural networks are used to select a suitable motion control pattern in actual environments. The back propagation algorithm adjusts the weights of the neural networks so that the selected motion control pattern corresponds to the action, which is obtained by the operator's behavior decision skill. To realize the selected motion control pattern, the orientation angle and the speed of the mobile robot are determined by fuzzy reasoning in which fuzzy rules are also automatically tuned so as to simulate the operator's control skill. We have implemented and tested the proposed control algorithm on an autonomous mobile robot and some experimental results demonstrate the effectiveness of the proposed control algorithm for the autonomous mobile robot. © 2000 Scripta Technica, Electr Eng Jpn, 131(2): 30–39, 2000