Faradaic impedance of dye-sensitized solar cells

Theoretical equations of the Faradaic impedance of the photoelectrode and the counter electrode of dye-sensitized solar cell (DSC) were derived. The Faradaic impedance is the frequency dependent resistance related to the time constants of elementary electrode processes like photoexcitation, electron transfer, charge transfer reaction and diffusion. The typical cell impedance spectrum describes the locus of three semicircles on the Nyquist plane. The locus of three semicircles is generally analyzed by using the equivalent circuit composed of charge transfer resistance (R_ct,1) and capacitance (C_dl,1) of counter electrode, charge transfer resistance (R_ct,2) and capacitance (C_dl,2) of photoelectrode, the finite diffusion impedance due to the diffusion of I₃⁻ on the counter electrode (Z_w), and total resistance of the substrate and solution (R_s). The physical meanings of R_ct,1 and R_ct,2 can be elucidated by the interpretations of Faradaic impedance derived in the present paper. The R_ct,1 is represented as the function of the potential-dependent rate constants of I₃⁻ reduction and I⁻ oxidation. On the other hand, the R_ct,2 is the function of the photoelectrode potential, the surface concentration of I₃⁻ and the potential-independent rate constant of the back electron transfer reaction. The theoretical expressions of the current-voltage (I-V) curve of the DSC can be also derived. In the present paper, the relations between the impedance and I-V curve of the DSC are discussed.     

Self-discharge behavior of polyacenic semiconductor and graphite negative electrodes for lithium-ion batteries

Variations in open-circuit potential (OCP) of artificial graphite and polyacenic semiconductor (PAS) negative electrodes have been investigated as a function of the storage time in alkylcarbonate-based electrolyte solutions after their cathodic charging (electrochemical lithiation) to discuss self-discharge phenomena of these negative electrodes for lithium ion batteries. The OCP of the graphite showed a plateau at ca. 90 mV vs. Li/Li⁺ for a long period (>8 × 10⁵ s), which suggested the retention of a stage structure of lithiated graphite during the storage. The lithiated PAS electrode gave gradual changes in OCP during the storage in the carbonate-based electrolyte solutions, suggesting continuous loss of Li species in the electrode. Variations in the interfacial resistance determined by an ac method, corresponding to the changes in the structure and properties at the electrode/electrolyte interface, also showed different features for the lithiated graphite and PAS electrodes. The mechanisms of self-discharging for these carbonaceous electrodes are discussed from the results of the influences of temperature and additives on the OCP variations.     

Relationship between structure and physical strength of silk fibroin nanofiber sheet depending on insolubilization treatment

Materials such as expanded polytetrafluoroethylene and glutaraldehyde‐fixed bovine pericardium are currently used for cardiac tissue regeneration. However, patches made from these materials remain permanently without being absorbed by the body and must be replaced overtime because of degeneration or lack of growth. To improve the long‐term outcomes for cardiac tissue regeneration, biocompatible and biodegradable materials must be used. In this study, we used two biocompatible polymers, silk fibroin (SF), which is biodegradable and segmented polyurethane, to prepare nonwoven sheets that were then insolubilized by water vapor or methanol treatment. The tensile stress increased significantly on adding segmented polyurethane to pure SF and the water vapor processed sheets showed higher extension on strain than the methanol‐processed sheets. The different insolubilization treatments also resulted in different SF structures. Our results show that it is possible to obtain the physical properties required for cardiac tissue repair patch by varying the insolubilization treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45560.     

Difference in environmental degradability between poly(ethylene succinate) and poly(3-hydroxybutyrate)

A chemosynthetic aliphatic polyester, poly(ethylene succinate) (PESu), was degraded by a poly(3-hydroxybutyrate) (P(3HB)) depolymerase in vitro. While P(3HB) exhibited good biodegradability in all environments, PESu hardly underwent biodegradation in a marine environment. To understand the difference in environmental degradability between PESu and P(3HB), we investigated the distribution of P(3HB)- and PESu-degrading microbes in various environments. PESu-degrading microbes were never detected in marine environments. PESu-degrading bacteria isolated from various environments in this study belonged to the phyla Firmicutes and Proteobacteria. Most PESu-degrading bacterial isolates could not degrade P(3HB), suggesting that PESu was not degraded by P(3HB) depolymerase in actual environments. In addition, all bacterial isolates that were screened for P(3HB) degrading activity from various environments in this study did not degrade PESu, suggesting that PESu does not induce P(3HB) depolymerase in their bacteria and P(3HB)-degrading bacteria are not involved in biodegradation of PESu in actual environments. Taken together, these results could be related with the low biodegradability of PESu in marine environments.     

Covalently cross-linked multilayer thin films composed of diazoresin and brilliant yellow for an optical pH sensor

The multilayered thin films composed diazoresin (DR) and brilliant yellow (BY) were fabricated by a layer-by-layer (LbL) deposition technique, and the ionic bonds between diazonium ion in DR and sulfonate residues in BY were converted to covalent bonds by UV light irradiation. The cross-linking between BY and DR prevented BY from desorption even in a pH 13 solution. The cross-linked (DR/BY)₁₀DR film exhibited pH-dependent absorption spectra in pH 9-13, and the response was repeatable and quick. The pH response time of the films was within a few seconds upon change from pH 9.0 to 13.0, and ca. 40 s upon change from pH 13.0 to 9.0.     

Immersion‐Angle Dependence of the Resonant‐Frequency Shift of a Quartz Crystal Microbalance in Three Types of Newtonian Liquids

Abstract

The present work reports the new characteristics of the immersion‐angle dependence of the resonant‐frequency shift (ΔF) of the one‐face sealed quartz crystal microbalance (QCM) in three types of Newtonian liquids, i.e., sucrose, glucose, and glycerol solutions. Below some 1.80×10^?2 g cm^?2 · s^?1/2, the ΔF values are dependent on the immersion angles in all solutions. However, we have found that the transition phenomenon of ΔF occurs between 1.78×10^?2 and 4.80×10^?2 g · cm^?2 · s^?1/2 in the sucrose solution, between 1.75×10^?2 and 4.34×10^?2 g · cm^?2 · s^?1/2 in the glucose solution and between 1.83×10^?2 and 3.03×10^?2 g · cm^?2 · s^?1/2 in the glycerol solution, respectively. Moreover, above the concentrations of the end points of the transition phenomenon, the ΔF values of the sucrose solution are equal to those of 90° at all immersion angles. On the other hand, those of the glucose and the glycerol solutions are the same as those of 30°. This difference may be caused by inherent characteristics of adsorption to the surface of the QCM electrode.     

Isolation and characterization of hardening-induced proteins in Chlorella vulgaris C-27: identification of late embryogenesis abundant proteins

Hardening-induced soluble proteins of Chlorella vulgaris Beijerink IAM C-27 (formerly Chlorella ellipsoidea Gerneck IAM C-27) were isolated and purified by two-dimensional high-performance liquid chromatography (2D-HPLC) on an anion-exchange column, with subsequent reversed-phase chromatography. Some of the proteins were resolved by SDS-PAGE, characterized by amino-terminal sequencing and identified by searching for homologies in databases. Separation of the soluble proteins during the hardening of Chlorella by a combination of 2D-HPLC and SDS-PAGE revealed that at least 31 proteins were induced or increased in abundance. Of particular interest was the induction after 12 h of a 10-kDa protein with the amino-terminal amino acid sequence AGNKPITEQISDAVGAAGQKVG and the induction after 6 h of a 14-kDa protein with the amino-terminal sequence ALGEESLGDKAKNAFEDAKDAVKDAAGNVKEAV. The amino-terminal sequences of these proteins indicated that they were homologous to late embryogenesis abundant (LEA) proteins. Furthermore, the level of a 22-kDa protein also increased after 12 h. The amino-terminal sequence of this protein, AAPLVGGPAPDFTAAAVFD, indicated that it was homologous to thioredoxin peroxidase.     

Michaelis-Menten analysis of immobilized enzyme by affinity capillary electrophoresis

Michaelis constant of enzymatic reaction was evaluated by affinity capillary electrophoresis using beta-galactosidase as a model enzyme and o- and p-isomers of nitrophenyl-beta-galactoside as substrates. The enzyme was immobilized on the inner surface of a fused-silica capillary by the covalent bonding through a bridging group, and the substrates were introduced into the capillary. The reaction products migrated electrophoretically toward the detection side (anodic side), while the unreacted substrates moved toward the injection side (cathodic side) on a slow electroosmotic flow generated by the weak negative charge of the immobilized enzyme. The initial velocity of the enzymatic reaction was estimated from the peak height of the product, and the Michaelis constant was calculated according to Lineweaver-Burk equation. The results (Km, 2.34 mM for o-isomer and 1.09 mM for p-isomer) were reproducible (RSD < 11.8%, n = 5). Although the estimated Michaelis constants were larger than the reported values measured in homogeneous solution, the ratio of the Michaelis constants of o-/p-isomers was in good agreement with the literature value. The present method required as low as a few microgram amount of enzyme and nanogram amount of substrate which is far smaller than those required in a conventional affinity HPLC.     

Subarachnoid haemorrhage induced proliferation of leptomeningeal cells and deposition of extracellular matrices in the arachnoid granulations and subarachnoid space. Immunhistochemical study

Subarachnoid haemorrhage (SAH) often leads to subarachnoid fibrosis and resultant normal pressure hydrocephalus; however, how subarachnoid fibrosis occurs is unknown. We examined the changes within arachnoid granulations (AGs) and the subarachnoid space (SAS) chronologically at the parasagittal region obtained from patients with SAH at autopsy and made comparison with controls by immunostaining for cytokeratin, specific marker for leptomeningeal cells and by the elastica Masson-Goldner methods. Within a week some AGs were torn, and many inflammatory cells filled the AGs and SAS. Cytokeratin positive cells were scarce. During the next two weeks cytokeratin positive cells increased. After three weeks, AGs and SAS were filled by dense deposits of extracellular matrices surrounded by multiple layers of leptomeningeal cells.