Electrochemical methods coupled with impedance measurement for energy gap study: correlation between the energy states and charge transport properties

The energy states of poly(3-hexylthiophene) (P3HT) polymer films degraded using UV/ozone environment were studied by optical and electrochemical methods. Energy levels of highest occupied and lowest unoccupied molecular orbitals as well as localized states between them were estimated. Electrical properties of polymer films sandwiched between two metal electrodes were investigated for various trap energy distributions. Comparison of the energy states density evaluated by optical/electrochemical methods and estimated from the current-voltage characteristics was carried out to discuss suitability of space-charge limited electrical conduction models for semiconducting polymers.     

ZEOLITE SYNTHESIS FROM PAPER SLUDGE ASH VIA ACID LEACHING

Paper sludge ash (PSA) typically has a low Si abundance and significant Ca content due to the presence of calcite fillers. Acid leaching with HCl was used to reduce the Ca content so that a zeolitic product with a high cation exchange capacity (CEC) could be synthesized. Zeolitic products were synthesized from raw ash and leached ash through reaction with 2.5 M NaOH solution at 80°C. In the case of the original ash without acid leaching, the concentration of Al in the alkali solution always exceeded that of Si during the synthesis, and hydroxysodalite with a low Si/Al ratio (1:1) was formed. In the case of the leached ash, the concentration of Si always exceeded that of Al during the synthesis, and zeolite-P with a higher Si/Al ratio (5:3) was formed. Hydroxysodalite and zeolite-P crystallization was saturated after 6 h of reaction, and the product from leached ash had a higher CEC (approximately 150 cmol/kg) than that from original ash (approximately 40 cmol/kg). Both the decrease in the Ca phase in the leached ash and the corresponding increase in the Si and Al amorphous phases play an important role in zeolite synthesis.     

Cloning and sequence analysis of D-erythrulose reductase from chicken: its close structural relation to tetrameric carbonyl reductases

Sequence analysis of a cDNA for D-erythrulose reductase fromchicken liver showed that the deduced open reading frame encodesthe protein with a molecular mass of 26 kDa consisting of 246amino acids. Although the reductase shares more than 60% identityin the amino acid sequence with the mouse tetrameric carbonylreductase, these two enzymes have many biochemical differences;their substrate specificity, subcellular localization, organdistribution, etc. A three-dimensional structure of D-erythrulosereductase was predicted by comparative modeling based on thestructure of the tetrameric carbonyl reductase (PDB entry =1CYD). Most of the residues at the active site (within 4 Åfrom the ligand) of the carbonyl reductase were also conservedin the D-erythrulose reductase. Nevertheless, Val190 and Leu146in the active site of the tetrameric carbonyl reductase weresubstituted in the D-erythrulose reductase by Asn192 and His148,respectively. The substitutions in the active sites may be relatedto the difference in substrate specificity of the two enzymes.The phylogenic analysis of D-erythrulose reductase and the otherrelated proteins suggests that the protein described as a carbonylreductase D-erythrulose reductase.     

Preparation of new heteronuclear (NH4)RE[FeII(CN)6]·nH2O complexes (RE = La,Ce, Pr,Nd, Sm,Gd, Dy,Y, Er,Lu) and their low-temperature decomposition for perovskite-type oxide

New heteronuclear (NH₄)RE^III[Fe^II(CN)₆]·nH₂O complexes (RE = La, Ce, Pr, Nd, Sm, Gd, Dy, Y, Er, Lu) were synthesized and their thermal decomposition products were investigated. The crystal structure of (NH₄)RE[Fe^II(CN)₆]·nH₂O would be a hexagonal unit cell (space group: P6₃/m), which was the same as that of La[Fe^III(CN)₆]·5H₂O. The hydration number n = 4 was estimated by TG results for all the RE complexes. The lattice constants depended on the ionic radius of the RE³⁺ ion for the heteronuclear complexes. The single phase of the perovskite type materials was directly obtained by decomposition of the heteronuclear complexes for RE = La, Pr, Nd, Sm, and Gd. A mixture of CeO₂ and Fe₂O₃ was formed for RE = Ce because of its oxidation to Ce⁴⁺. In the case of RE = Dy, Y, Er, and Lu complexes, the perovskite type materials formed at higher temperature via. mixed oxides such as RE₂O₃ and RE₄Fe₅O₁₃ due to the small RE³⁺ ionic radius.     

Crystallization of lead zirconate titanate without passing through pyrochlore by new solution process

We report a novel low-temperature crystallization path for perovskite lead zirconate titanate (PZT) from solution. The modification of a PZT solution by monoethanolamine (MEA) resulted in a change in the crystallization behavior. MEA was strongly coordinated to the metal ions, resulting in destroy of multinuclear metal organic complexes. This led to a remarkably increased pyrolysis temperature, and Pb²⁺ was reduced into Pb⁰ because of a reducing environment at 200–300 °C. Nanoscopic separations of Pb⁰ was later transformed into uniformly distributed α-PbO nanocrystals and clusters in the amorphous Zr/Ti–O matrix, and finally the sample crystallized into perovskite at 400–500 °C. On the other hand, pyrochlore phase was observed in the conventional crystallization process. The avoidance of pyrochlore formation is the key for the low-temperature crystallization of perovskite. X-ray absorption fine structure (XAFS) analysis was performed to reveal the structures in solutions and amorphous phases.     

Conformation-dependent dynamics of macromolecular ions in the gas phase under an electrostatic field: A molecular dynamics simulation

Highly charged macromolecular ions exhibit various conformations in gas. Intramolecular charge-to-charge interaction induces a transformation from a globular structure into a stretched one. The change in the molecular conformation brings a complex dynamic behavior of ions under an electrostatic field. In the present study, we visualized the movement of a monovalent and multiply charged straight chain macromolecules, polyethylene glycol (PEG), by a molecular dynamics (MD) simulation. The simulation showed that a singly charged PEG ion (899?<?M_W < 4,643) takes a globular conformation. The electrical mobilities of these ions determined from the migration distance under an electric field were compared with the experimental data and those determined by the classical Mason–Schamp theory under an assumption of spherical shape. As a result, we obtained a good agreement between the MD, theoretical, and experimental data for the monovalent ions. We also found that the MD simulation successfully predicts the electrical mobility of the multiply charged stretched PEG ions, but the classical theory fails. We were able to visualize the periodic bending and stretching motion by the MD simulation. This unique motion results from the localization of charges on the PEG molecule and may have a significant effect on the dynamic behavior of macromolecule ions in gas.

Copyright © 2019 American Association for Aerosol Research     

Thermionic emission model for contact resistance in organic field-effect transistor

Injection mechanism of top-contact pentacene field-effect transistor (OFET) was investigated in respect to the internal field. The contact resistance was evaluated by the transmission line method for various applied external voltages as well as various pentacene film thicknesses. The behaviour of contact resistance was described in terms of the thermionic emission model (Schottky injection) and internal electric field generated by excess charges accumulated on pentacene–gate insulator interface. It was shown that pentacene film thickness changes the internal electric field affecting the carrier injection barrier. It was concluded that the space-charge field effect made a significant contribution for smaller pentacene film thicknesses and therefore in accordance to the thermionic model was able to decrease contact resistance representing the potential drop.     

On-chip encapsulation of lipase using mesoporous silica: A new route to enzyme microreactors

A polydimethylsiloxane/glass microfluidic reactor containing lipase-mesoporous silica (FSM-22) conjugates has been successfully constructed without chemical cross-linking between enzyme and support. A direct visualization of conjugates of lipase and FSM-22 immobilized in the microreactor by optical microscopy revealed that the enzymes were uniformly dispersed throughout the particles of the FSM-22, because of the successful immobilization of the enzyme. Moreover, the lipase-FSM-22 conjugates contained in the microreactor indicated higher enzymatic activity in hydrolysis of triglyceride, as compared with a batch experiment. These results demonstrate that the microreactor using mesoporous silica performs not only the reagent-less enzyme immobilization but also the high reactivity of the enzyme.