Electrochemical examination of the ascorbic acid radical anion in non-aqueous electrolytes

A quasi-reversible redox reaction involving ascorbic acid was observed in non-aqueous electrolytes at conductive diamond electrode. The chemical reversibility of these reactions is consistent with ascorbic acid being reduced to the ascorbic acid radical anion in a one-electron process, with subsequent reoxidation to ascorbic acid. This is the first report on the electrochemical production of the ascorbic acid radical anion in non-aqueous electrolytes. Ascorbyl 6-stearate and 4-hydroxy 2(5H)-furanone, which have somewhat similar structures as ascorbic acid, also showed one-electron transfer reduction reaction producing radicals with a single negative charge, suggesting that these compounds follow the same electrochemical behavior as ascorbic acid. The double bond and hydroxyl substituent on the five-membered ring are shown to be necessary for the stabilization of the radical anions. It was confirmed by the calculation of the total energy using molecular orbital methods that resonance structures involving the double-bond and hydroxyl group provide significant stabilization of the radical anions. Electrochemical preparation may be a useful method for the detailed study of radicals, their molecular structure and reactivity.     

Chemical‐Free Approach for Z‐Isomerization of Lycopene in Tomato Powder: Hot Air and Superheated Steam Heating above the Melting Point of Lycopene

Z‐isomers of lycopene exhibit higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. Therefore, it is important to develop an efficient and environmentally friendly procedure for Z‐isomerization. The current methods for Z‐isomerization of (all‐E)‐lycopene use toxic chemicals such as organic solvents and catalysts. This study is aimed to develop a chemical‐free method for Z‐isomerization of (all‐E)‐lycopene in tomato powder by hot air and superheated steam heating. The Z‐isomerization reaction is promoted by heating above the melting point of lycopene. When heated with superheated steam, the thermal decomposition of lycopene is suppressed compared to that when heated with hot air. When tomato powder is heated at 240 °C for 5 min by superheated steam, the total Z‐isomer content and remaining lycopene are 69.0% and 90.7%, respectively, while with hot air heating, the total Z‐isomer content and remaining lycopene are 69.9% and 68.0%, respectively. These results indicate that the thermal Z‐isomerization of lycopene occurs in the molten state and heating in a low oxygen atmosphere suppresses the thermal decomposition of lycopene. Practical Applications: Tomato powder rich in lycopene Z‐isomers is an important ingredient for the food and animal feed industries. Since Z‐isomers of lycopene are more soluble in solvents including ethanol which is a low‐toxicity and environmentally friendly solvent, the efficiency of lycopene extraction with ethanol can be improved by using the Z‐isomer‐rich tomato powder as a raw material. The obtained Z‐isomer‐rich extract has a high added value because the Z‐isomers have higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. In addition, since lycopene Z‐isomers exhibit higher accumulation efficiency and better color improvement in hen egg yolks than those of the all‐E‐isomer, Z‐isomer‐rich tomato powder is an effective animal feed.     

Surface-collection efficiency of Nuclepore filters for nanoparticles

The flat surface of Nuclepore filters is suitable for observing collected particles with a scanning electron microscope (SEM). However, experimental data on surface-collection efficiency are limited because surface-collection efficiencies cannot be measured directly using aerosol measuring instruments. In this study, the surface-collection efficiencies of Nuclepore filters were determined by establishing the ratio of the number of particles deposited on the surface of the filter visually counted with an SEM to the number of inflow particles counted by a condensation particle counter, using monodispersed polystyrene latex particles (30–800 nm) and silver particles (15–30 nm). Because Nuclepore filters with smaller pore sizes would be expected to produce higher minimum surface-collection efficiency and a higher pressure-drop, 0.08 and 0.2 µm Nuclepore filters were chosen as the test filters in view of both collection efficiency and pressure drop. The results showed that the minimum surface-collection efficiencies of the 0.08 µm pores at face velocities of 1.9 and 8.4 cm·s^?1 were approximately 0.6 and 0.7, respectively, and those of the 0.2 µm pores at face velocities of 1.5 and 8.6 cm·s^?1 were approximately 0.8 and 0.6, respectively. Because the pressure drop of the 0.2 µm pore filter was lower than that of the 0.08 µm pore filter under the same flow-rate conditions, the 0.2 µm pore filter would be more suitable considering the pressure drop and collection efficiency. The obtained surface collection efficiencies were quantitatively inconsistent with theoretical surface-collection efficiencies calculated using conventional theoretical models developed to determine the collection efficiency of filters with larger pores.

© 2016 American Association for Aerosol Research     

Producing gear teeth with high form accuracy and fine surface finish using water-lubricated chemical reactions

A new method was investigated for high-accuracy fine finishing of gear teeth surfaces using a water-lubricated tribo-chemical technique. A pair of shaved gears with rather low surface roughness was rotated in water lubricant for 30 min so that the gear tooth surface contacting the mating tooth was ‘worn’ to a mirror surface and ideal tooth profile, due to the mechano-chemical mild erosion of the contact area. The wear rate was 2.0 μm per 20,000 meshings, corresponding to a wear of one atomic radius thickness per meshing. Oxidation of the steel surface by water molecules is proposed as the dominant wear process. Operation noise from the gear pair rotation was drastically reduced to lower than about 10–15 dB compared to conventionally machined gear surfaces (30 dB in average), as a result of the wear of the tooth surface to form a best-fit profile. The noise increased with further processing of the gear pair. Thus, there is an appropriate number of rotations for suitable surface wear treatment. This new and simple procedure for surface treatment assures saving in energy, and does not require expensive honing techniques or high-accuracy grinding tools.The wear mechanisms used in this process are discussed along with the application of the technique to other processes for precision finishing.     

Transparent Hydroxyapatite Prepared by Hot Isostatic Pressing of Filter Cake

Hydroxyapatite powder was synthesized and formed into a compact in an aqueous medium using a filter-cake method. The compact was hot isostatically pressed at 700° to 1000°C and 100 MPa for 2 h. Fully dense, transparent materials were obtained above 800°C. Both forming and densification methods were found to be important in obtaining transparent materials.     

Chemical and Chromatic Bases for Preferential Visiting By the Cabbage Butterfly, Pieris rapae, to Rape Flowers

Scent and coloration of corolla were examined as floral attributes responsible for preferential visiting by the cabbage butterfly, Pieris rapae, to rape flower, Brassica rapa. Floral volatile components that release the flower-visiting behavior of the butterfly were identified by chemical analyses, electroantennography (EAG), and two behavioral bioassays: proboscis extension reflex (PER) in response to odor and attraction to artificial flowers. GC and GC-MS analyses of the headspace volatiles from the flowers revealed the presence of six aromatic compounds, benzaldehyde, phenylacetaldehyde, benzyl alcohol, 2-phenylethanol, phenylacetonitrile, and indole in decreasing order of quantity. Of these, phenylacetaldehyde elicited the highest response in the PER assay. While benzyl alcohol, 2-phenylethanol, benzaldehyde, and phenylacetonitrile evoked moderate responses, the PER-eliciting activity of indole was very weak. In two-choice behavioral bioassays, artificial flowers scented with any one of these PER-active compounds attracted significantly more butterflies than control (unscented) flowers, whereas those treated with indole were almost inactive. The EAG activities of the six chemicals were not high and were about the same at a low dose (1 g), but phenylacetaldehyde elicited a much stronger response from both sexes at higher doses (10 and 100 g). An overall profile of EAG responses at a dose of 100 g was analogous to that of PER performance, suggesting that floral volatiles may be involved in close-range location or recognition of flowers rather than long-range attraction. By spectroscopic and UV-photographic examinations of rape flower, the central part of the corolla was found to absorb UV rays in marked contrast to the other parts, which reflected near-UV rays (_max = 350 nm). This indicates that the flower is endowed with a conspicuous nectar guide that is probably an important visual stimulus for attracting foraging adults of P. rapae. Consequently, the present findings strongly suggest that this elaborate pollination strategy of rape flower, characterized by its good combination of olfactory and visual attractiveness, accounts for preferential visiting by the cabbage butterfly to the flower.     

Effect of chemical composition on anode area formation in TIG arc welding. Effect of chemical composition on weldability in fabrication in high alloyed steel (1st Report)

Summary

This paper describes a fundamental investigation of the weldability of A5052 wrought alloy and AC7A castings in electron beam welding and gas tungsten arc welding. Microscopic observations, hardness, tensile, and impact tests were used. In electron beam welding, the tensile and impact properties of the wrought alloy weld metal and heat affected zone are satisfactory. Micro-solidification cracks are found in the weld metal, whereas micro-liquation cracks are found in the AC7A HAZ. The tensile properties of the welds produced by GTAW (or TIG) are virtually equivalent or slightly inferior to those of the electron beam welded joints.     

Kinetic analysis of crystallization of zeolite beta synthesized by direct heating

To quantitatively investigate the initial crystallization of zeolite beta synthesized by direct heating, the extent of the reaction was precisely evaluated by X-ray diffraction measurements and Rietveld structural refinement, and a kinetic analysis of crystallization was performed using the Avrami-Erofe'ev equation. The activation energy for crystallization was lower than that for hydrothermal synthesis. Reaction and synthesis time curves revealed that the initial zeolite beta crystallization consisted of three stages. The first was an induction period with nucleation by the generation of building units and the formation of an initial coordinated structure. The second stage was crystal growth by a diffusion-controlled reaction, and the third stage involved slowing down of crystallization by the limitation of dehydrocondensation. These stages could be analyzed by calculation of the rate constant and Avrami exponent for each stage.