Performance decay of proton-exchange membrane fuel cells under open circuit conditions induced by membrane decomposition

The degradation in performance of proton-exchange membrane fuel cells (PEMFCs) under open circuit conditions was investigated. The oxygen reduction reaction (ORR) kinetic current density at 0.9 V was found to decrease from 36 to 4 mA cm⁻² (geometric) without significant crossover increase or loss in the electrochemically active surface area. Cyclic voltammograms for the electrodes show characteristic changes, e.g. appearance of peaks at ∼0.2 V and shift of the onset of platinum oxide formation to higher potentials. It was identified that the large ORR kinetic decay has its origins in the reduction of available Pt sites due to adsorption of anions, which are postulated to be membrane decomposition products such as sulfate ions. Procedures carried out to condense water in the fuel cell led to the expulsion of anions out of the membrane electrode assembly (MEA) resulting in the partial recovery of ORR kinetic current density to 15 mA cm⁻². In order to attain complete performance recovery of the catalyst, a more effective and practical method to flush out the anions is desirable.     

The impact of air contaminants on PEMFC performance and durability

The impact of air contaminants such as sulfur compounds (SO₂, H₂S) and nitrogen compounds (NO_x and NH₃) was investigated using subscale fuel cells. The severity of the effect of these impurities varies depending on the contaminants. Among air contaminants, sulfur compounds cause the most severe performance loss due to decrease of available Pt sites for oxygen reduction reaction (ORR). We found that sulfur compounds adsorbed on Pt surface tend to be oxidized to sulfate at 0.9 V and higher potentials. The cell performance can be recovered partially by excursions to high potentials due to increase of available Pt sites. Furthermore, flushing the cathode with high humidity gases results in almost complete recovery of the cell performance. We conclude that these recovery effects are due to oxidation/removal of the contaminants from the Pt surface.     

A Breath Ammonia Sensor Based on Conducting Polymer Nanojunctions

We present an ammonia sensor for human breath analysis based on electrically conducting polymer nanojunctions. Each nanojunction is formed by bridging a pair of gold nanoelectrodes on a silicon chip separated by a small gap (<60 nm) with electrodeposited polyaniline. The signal transduction mechanism of the sensor is the change in the nanojunction conductance as a result of polymer dedoping by ammonia. The sensor response to human breath is validated by comparison with a reference method for detection of ammonium ion combined with an optimized breath ammonia trapping system. The nanojunction sensor is capable of in situ detection of parts per billion (ppb) levels of ammonia in human breath.     

mRNA expression induced by cell-substrate interaction. A two-dimensional tissue formation process

This study aimed to develop a quantitative assay method of determining cellular events at the mRNA level during tissue formation. Quantitative assessment of mRNAs coding specific proteins (beta-actin, fibronectin, laminin) during tissue formation on tissue culture dishes was attained using a Northern blot technique with autoradiography. The amount of beta-actin mRNA, the expression of which is initiated shortly after adhesion, greatly increased with incubation time and reached maximal levels near the confluent state, followed by a reduced expression at a later stage of tissue formation. The time course of beta-actin mRNA expression, which reflects cytoskeletal organization, corresponded well to morphologic changes in adherent cells. Expression of mRNAs coding the extracellular matrix proteins, fibronectin and laminin, was initiated at the proliferation stage. After maximum expression levels were observed at the confluent stage, a gradual decrease in the expression of both mRNAs was seen after longer culture periods. Expression patterns of mRNAs coding cytoskeletal and extracellular matrix proteins greatly depended upon the type of artificial substrates. Thus, the dynamic changes in tissue formation were quantified to elucidate the significance of artificial substrates in tissue formation at the mRNA level.     

A 16-Mb Toggle MRAM With Burst Modes

This paper describes a recently developed 16-Mb toggle magnetic random access memory (MRAM). It has 100-MHz burst modes that are compatible with a pseudo-SRAM even though the toggle cell requires reading and comparing sequences in write modes. To accelerate operating clock frequency, we propose a distributed-driver wide-swing current-mirror scheme, an interleaved and pipelined memory-array group activation scheme, and a noise-insulation switch scheme. These circuit schemes compensate the toggle cell timing overhead in write modes and maintain write-current precision that is essential for the wide operational margin of MRAMs. Because toggle cells are very resistant to write disturbance errors, we designed the 16-Mb MRAM to include a toggle MRAM cell. The MRAM was fabricated with 0.13-mum CMOS and 0.24-mum MRAM processes with five metal layers.     

Electrochemical deposition of molecular adsorbates for in situ scanning probe microscopy

We have studied gold and graphite electrodes in an electrochemistry cell under various solutions using the scanning tunneling microscope (STM). The gold (111) surface yields quite reproducible images and cyclic voltammograms. In situ voltammograms show that, under certain conditions, nanomolar quantities of DNA fragments can suppress the adsorption of a buffer salt of millimolar concentration. When the DNA concentration is reduced below that required for a monolayer coverage, the salt adsorption is restored. We show images of bare gold, gold covered with an adsorbate produced by the buffer salt, and gold prepared with a concentration of DNA fragments close to that required for monolayer coverage added to the buffer. Under these conditions, the surface is found to be uniformly covered with a characteristic structure.     

Development of a new advanced process for manufacturing polyacetal resins. Part III. End-capping during polymerization for manufacturing acetal homopolymer and copolymer

Conventionally, acetal homopolymer or copolymer is obtained by the polymerization of formaldehyde or trioxane, following the end-capping using acetic anhydride or unzipping of the unstable polymer end fraction. First, Asahi Chemical developed a new process to obtain an end-capped polymer during polymerization of highly purified formaldehyde using acetic anhydride as the chain-transfer agent. Use of highly purified formaldehyde and endcapping during polymerization using acetic anhydride as a chain-transfer agent or an endcapping agent will provide a simple process for manufacturing acetal homopolymer. The polymerization mechanism was confirmed by infrared spectroscopy analysis and proton NMR analysis of the polymer obtained. Second, for the acetal copolymer, purified trioxane was copolymerized with ethylene oxide in the presence of methylal, which gave an endcapped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated and a new initiation mechanism was proposed. © 1993 John Wiley & Sons, Inc.     

Transduction of full-length TAT fusion proteins into mammalian cells: TAT-p27Kip1 induces cell migration

Human procathepsin L has been expressed in E. coli in the form of inclusion bodies. The recombinant protein was isolated, refolded and processed at pH 5.5 by the addition of dextran sulfate which increased the overall yield of cathepsin L almost 10-fold. After the auto-activation of the 38 kDa procathepsin L at least three processing sites were determined by N-terminal amino acid sequencing. After replacing the Ala205 residue by glutamic acid, cathepsin B-like specificity was introduced into cathepsin L. This mutation resulted in a 15-fold increased activity toward the substrate Z-Arg-Arg-AMC and in a 29-fold decreased activity toward Z-Phe-Arg-AMC. Residue 205 is thereby confirmed experimentally to be critical for the specificity of cathepsins B and L.     

Peptidergic innervation in human von Ebner''s glands: an immunohistochemical study

Human bites in cases of homicide, sexual assault, and abuse are often distorted due to the elasticity and curvature of the skin. Physical comparison of a bite mark to a suspect's teeth is sometimes difficult. Saliva, which is usually deposited during biting, can be collected and analyzed to identify the perpetrator. Using simulated bite mark situations in two experimental series, three samples of 40 microL of whole saliva were deposited on the skin of 27 cadavers (at 33 sites) and three samples of 100 microL of whole saliva were deposited on the skin of 5 cadavers (at 12 sites). Saliva was collected using the double swab technique at t = 5 min, t = 24 h, and t = 48 h. DNA was extracted using the modified Chelex method and submitted to PCR-based typing at two short tandem repeat loci. Results indicate that the concentration of DNA in saliva recovered from skin varies as a function of time since deposition. There is a significant decrease in concentration in the first 24 h but the concentration remains stable from 24 to 48 h. The success of PCR amplification is independent of the time since deposition or the concentration of DNA in the saliva sample. Contamination from the DNA of the cadaver was not found in any of the cases studied.     

Laser-induced shockwave chromatography: a separation and analysis method for nanometer-sized particles and molecules

A microscopic chromatography has been developed where nanometer-size molecules or particles are separated according to their size by the laser-induced shockwave in a water-filled capillary. As the shockwave passed through the mixture of molecules/particles in solution, they move to the direction of the propagation of the shockwave. The distance from the point of shockwave generation depends on the particle size or molecular weight. This technique has some advantages compared to conventional chromatography, in terms of quick analysis of molecular weight and applicability to sticky and adsorbing polymers. Experimental results obtained for proteins, their aggregates, and inorganic nanoparticles are presented.