A double logarithmic method in thin-layer spectroelectrochemistry for distinction among mechanisms of an irreversible electrochemical process

A simple double logarithmic method in potential-controlled thin-layer spectroelectrochemistry for an irreversible electrochemical process has been studied by numerical analysis and examined by experimental examples. This simple algorithm has a novel function offering some important information about the mechanism of a complex electrochemical process directly from a limited amount of potential-spectrum data, and can be used to distinguish different reaction mechanisms such as E, EC, EE, as well as to determine the electron-transfer coefficient, a, and the kinetically modified E-0'. Combination of the double logarithmic method with nonlinear regression provides a powerful tool to examine the proposed mechanism and also to estimate other thermodynamic and kinetic parameters. (C) 1999 The Electrochemical Society. S0013-4651(98)06-090-X. All rights reserved.

Mesofracture mechanics: a necessary link

Classical fracture mechanics is based on the premise that small scale features could be averaged to give a larger scale property such that the assumption of material homogeneity would hold. Involvement of the material microstructure, however, necessitates different characteristic lengths for describing different geometric features. Macroscopic parameters could not be freely exchanged with those at the microscopic scale level. Such a practice could cause misinterpretation of test data. Ambiguities arising from the lack of a more precise range of limitations for the definitions of physical parameters are discussed in connection with material length scales. Physical events overlooked between the macroscopic and microscopic scale could be the link that is needed to bridge the gap. The classical models for the creation of free surface for a liquid and solid are oversimplified. They consider only the translational motion of individual atoms. Movements of groups or clusters of molecules deserve attention. Multiscale cracking behavior also requires the distinction of material damage involving at least two different scales in a single simulation. In this connection, special attention should be given to the use of asymptotic solution in contrast to the full field solution when applying fracture criteria. The former may leave out detail features that would have otherwise been included by the latter. Illustrations are provided for predicting the crack initiation sites of piezoceramics. No definite conclusions can be drawn from the atomistic simulation models such as those used in molecular dynamics until the non-equilibrium boundary conditions can be better understood. The specification of strain rates and temperatures should be synchronized as the specimen size is reduced to microns. Many of the results obtained at the atomic scale should be first identified with those at the mesoscale before they are assumed to be connected with macroscopic observations. Hopefully, "mesofracture mechanics" could serve as the link to bring macrofracture mechanics closer to microfracture mechanics.

Fracture statistics of brittle materials: Weibull or normal distribution

The fit of fracture strength data of brittle materials (Si3N4, SiC, and ZnO) to the Weibull and normal distributions is compared in terms of the Akaike information criterion. For Si3N4, the Weibull distribution fits the data better than the normal distribution, but for ZnO the result is just the opposite. In the case of SiC, the difference is not large enough to make a clear distinction between the two distributions. There is not sufficient evidence to show that the Weibull distribution is always preferred to other distributions, and the uncritical use of the Weibull distribution for strength data is questioned.

Electromagnetic fields and transmission properties in tapered hollow metallic waveguides

We analyze the electromagnetic spatital distributions and address an important issue of the transmission properties of spherical transverse-electric (TE) and transverse-magnetic (TM) eigenmodes within a tapered hollow metallic waveguide in detail. Explicit analytical expressions for the spatital distributions of electromagnetic field components, attenuation constant, phase constant and wave impedance are derived. Accurate eigenvalues obtained numerically are used to study the dependences of the transmission properties on the taper angle, the mode as well as the length of the waveguide. It is shown that all modes run continuously from a propagating through a transition to an evanescent region and the value of the attenuation increases as the distance from the cone vertex and the cone angle decrease. A strict distinction between pure propagating and pure evanescent modes cannot be achieved. One mode after the other reaches cutoff in the tapered hollow metallic waveguide as the distance from the cone vertex desreases. (C) 2008 Optical Society of America

Population structure and history in East Asia

Archaeological, anatomical, linguistic, and genetic data have suggested that there is an old and significant boundary between the populations of north and south China. We use three human genetic marker systems and one human-carried virus to examine the north/south distinction. We find no support for a major north/south division in these markers; rather, the marker patterns suggest simple isolation by distance.

Morphological variability between wild populations and inbred stocks of a Chinese minnow, Gobiocypris rarus

Gobiocypris rarus, a small, native cyprinid fish, is currently widely used in research on fish pathology, genetics, toxicology, embryology, and physiology in China. To develop this species as a model laboratory animal, inbred strains have been successfully created. In this study, to explore a method to discriminate inbred strains and evaluate inbreeding effects, morphological variation among three wild populations and three inbred stocks of G. rarus was investigated by the multivariate analysis of eight meristic and 30 morphometric characters. Tiny intraspecific variations in meristic characters were found, but these were not effective for population distinction. Stepwise discriminant analysis and cluster analysis of conventional measures and truss network data showed considerabe divergence among populations, especially between wild populations and inbred stocks. The average discriminant accuracy for all populations was 82.1% based on conventional measures and 86.4% based on truss data, whereas the discriminant accuracy for inbred strains was much higher. These results suggested that multivariate analyses of morphometric characters are an effective method for discriminating inbred strains of G. rarus. Morphological differences between wild populations and inbred strains appear to result from both genetic differences and environmental factors. Thirteen characters, extracted from stepwise discriminant analysis, played important roles in morphological differentiation. These characters were mainly measures related to body depth and head size.

Taxonomic revision of water-bloom-forming species of oscillatorioid cyanobacteria

A polyphasic approach was used to clarify the taxonomy of the water-bloom-forming oscillatorioid cyanobacteria. Seventy-five strains of oscillatorioid cyanobacteria were characterized by 16S rDNA sequence analysis, DNA base composition, DNA-DNA hybridization, fatty acid composition, phycobilin pigment composition, complementary chromatic adaptation, morphological characters, growth temperature and salinity tolerance. Phylogenetic analysis based on 165 rDNA sequences divided the strains into six groups, all of which were clearly separated from the type species of the genus Oscillatoria, Oscillatoria princeps Gomont NIVA CYA 150. Therefore, these strains should be classified into genera other than Oscillatoria. Groups I-III were closely related to one another and groups IV-VI were distinct from one another and from groups I to III. Group I was further divided into two subgroups, group I-pc, which includes strains containing only phycocyanin (PC), and group I-pe, which includes strains containing large amounts of phycoerythrin (PE) in addition to PC. This phenotypic distinction was supported by DNA-DNA hybridization studies. Based on the properties examined herein and data from traditional, botanical taxonomic studies, the groups and subgroups were classified into single species and we propose either emended or new taxonomic descriptions for Planktothrix agardhii (type strain NIES 204(T)), Planktothrix rubescens (type strain CCAP 1459/22(T)) Planktothrix pseudagardhii sp. nov. (type strain T1-8-4(T)), Planktothrix mougeotii (type strain TR1-5(T)), Planktothricoides raciborskii gen. nov., comb. nov. (type strain NIES 207(T)), Tychonema bourrellyi (type strain CCAP 1459/11B(T)) and Limnothrix redekei (type strain NIVA CYA 277/1(T)).

One-dimensional modulation instability of broad optical beams in biased photorefractive-photovoltaic crystals under steady-state conditions

We present a comprehensive study of the one-dimensional modulation instability of broad optical beams in biased photo refractive-photovoltaic crystals under steady-state conditions. We obtain the one-dimensional modulation instability growth rate by globally treating the space-charge field and by considering distinction between values of Eo in nonlocal effects and local effects in the space-charge field, where Eo is the field constant correlated with terms in the space-charge field, which depends on the external bias field, the bulk photovoltaic effect, and the ratio of the optical beam's intensity to that of the dark irradiance. The one-dimensional modulation instability growth rate in local effects can be determined from that in nonlocal effects. When the bulk photovoltaic effect is neglectable, irrespective of distinction between values of Eo in nonlocal effects and local effects in the space-charge field, the one-dimensional modulation instability growth rates in nonlocal effects and local effects are those of broad optical beams studied previously in biased photorefractive-nonphotovoltaic crystals. When the external bias field is absent, the one-dimensional modulation instability growth rates in nonlocal effects and local effects predict those of broad optical beams in open- and closed-circuit photorefractive-photovoltaic crystals. (c) 2004 Elsevier B.V. All rights reserved.

Method for calculating ecological water storage and ecological water requirement of marsh

As one of the most typical wetlands, marsh plays an important role in hydrological and economic aspects, especially in keeping biological diversity. In this study, the definition and connotation of the ecological water storage of marsh is discussed for the first time, and its distinction and relationship with ecological water requirement are also analyzed. Furthermore, the gist and method of calculating ecological water storage and ecological water requirement have been provided, and Momoge wetland has been given as an example of calculation of the two variables. Ecological water use of marsh can be ascertained according to ecological water storage and ecological water requirement. For reasonably spatial and temporal variation of water storage and rational water resources planning, the suitable quantity of water supply to marsh can be calculated according to the hydrological conditions, ecological demand and actual water resources.

Self-assembled monolayer growth of phospholipids on hydrophobic surface toward mimetic biomembranes: Scanning probe microscopy study

Atomic force microscopy (AFM) and lateral force microscopy (LFM) were used simultaneously to analyze a model membrane bilayer structure consisting of a phospholipid outer monolayer deposited onto organosilane-derivatized mica surfaces, which were constructed by using painting and self-assembly methods. The phospholipid used as outer monolayer was dimyristoylphosphatidylcholine (DMPC). The hydrocarbon-covered substrate that formed the inner half bilayer was composed of a self-assembly monolayer (SAM) of octadecyltrichloroorganosilane (OTS) on mica. SAMs of DMPC were formed by exposing hydrophobic mica to a solution of DMPC in decane/isobutanol and subsequently immersing into pure water. AFM images of samples immersed in solution for varying exposure times showed that before forming a complete monolayer the molecules aggregated into dense islands (2.2-2.6 nm high) on the surface. The islands had a compact and rounded morphology. LFM, coupled with topographic data obtained with the atomic force mode, had made possible the distinction between DMPC and OTS. The rate constant of DMPC growth was calculated. This is the first systematic study of the SAM formation of DMPC by AFM and LFM imaging. It reveals more direct information about the film morphology than previous studies with conventional surface analytical techniques such as infrared spectroscopy, X-ray, or fluorescence microscopy.

Studies on the solution structures of lanthanide(III) complexes of DTPA-BIN by NMR

The solution structures of diamagnetic lanthanide (III) complexes of DTPA-BIN (Ln = La, Y, Lu, Sc) have been investigated by H-1 NMR, C-13 NMR and 2D NMR. For each complex, two or more species of asymmetric conformations with little distinction were identified at room temperature. And their solution structures vary with the radius of the central metals. NMR spectra support the hypothesis that Sc3+ with smaller radius formed an eight-coordinated structure with DTPA-BIN, La3+ with larger radius formed nine- or ten-coordinated structures with DTPA-BIN, and Y (DTPA-BIN) and Lu (DTPA-BIN) had nine-coordinated solution structures. The solution structure of Gd (DTPA-BIN) was obtained from the similarity of radius between Gd3+ and Y3+, which is a nine-coordinated structure formed by three nitrogens, three acetate oxygens, two acetyl oxygens, one water molecule and a gadolinium(III) cation.

Positive- and negative-ion matrix-assisted laser desorption/ionization mass spectrometry of saccharides

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) of oligosaccharides and polysaccharides has been investigated in detail, It is demonstrated that cationized species of oligosaccharides, [M+Na](+) and [M+K](+), are dominant products under the MALDI condition, and negative ions of oligosaccharides are not formed to any significant extent in this process, The molecular masses of polysaccharides are similarly determined by positive- and negative-ion MALDI-MS with the help of column chromatography. The distinction between positive- and negative-ion MALDI mass spectra of oligo-and polysaccharides indicates that the MALDI processes for saccharides vary with molecular mass. The matrix plays a more important role in the ionization process for oligosaccharides, while in the desorption process for polysaccharides. (C) 1998 John Wiley & Sons, Ltd.

Mass spectral study of extractable La- and Lu-containing fullerenes

Mass spectra of LaxC2n (x = 1,2), well known endohedral metallofullerenes, and Lu2C2n (2n = 76-112), new members of extractable metallofullerenes, were studied. Positive-ion laser desorption/ionization (LDI) and electron impact (EI) mass spectra indicated that lutetium is a special lanthanide that prefers to form dilutetium fullerenes by the are-burning method. However, the signals for Lu2C2n become very weak in negative-ion LDI-MS, this is different from La-2@C-80, which has close relative abundances in positive- and negative-ion MS. The distinction between Lu2C2n and La-2@C-80 in the negative-ion LDI mass spectra may be due to the different structures of La- and Lu-containing fullerenes. (C) 1997 by John Wiley & Sons, Ltd.