Potentiometric and spectrophotometric flow-injection determinations of metal ions with use of metal ion buffers

Potentiometric and spectrophotometric flow-injection determinations of metal ions, based on metal ion buffers, are described. A copper(II) ion-selective electrode and copper(II) ion buffers containing nitrilotriacetic acid (NTA) or ethylenebis(oxyethylenedinitrilo)tetraacetic acid (EGTA) are used for determination of ca. 10^?3 M transition metal ions or of calcium in the presence of magnesium. Spectrophotometric determination of transition metal ions is achieved by using a zinc ion buffer solution containing NTA and xylenol orange as indicator. Zinc concentrations up to 2 M can be determined by using large dispersion in the manifold. The factors influencing the sensitivity of the proposed methods are discussed.     

Sequential injection immunoassay for environmental measurements

Sequential injection immunoassay systems for environmental measurements based on the selective immunoreaction between antigen and antibody were described. A sequential injection analysis (SIA) technique is suitable to be applied for the procedure of enzyme-linked immunosorbent assay (ELISA), because the washing and the addition of reagent solutions can be automated by using a computer-controlled syringe pump and switching valve. We selected vitellogenin (Vg), which is a biomarker for evaluating environmental risk caused by endocrine-disrupting chemicals in the hydrosphere, and linear alkylbenzene sulfonates (LAS) and alkylphenol polyethoxylates (APEO), which are versatile surfactants, as target analytes in the flow immunoassay systems. For Vg monitoring, SIA systems based on spectrophotometric, chemiluminescence, and electrochemical determinations were constructed. On the other hand, chemiluminescence determination was applied to the detection of LAS and APEO. For APEO, an SIA system combined with surface plasmon resonance (SPR) sensor was also developed. These new sequential injection immunoassay systems are expected to be useful systems for environmental analysis.     

Differential Effects of Cold Exposure on Gene Expression Profiles in White Versus Brown Adipose Tissue

The thermogenic function of brown adipose tissue (BAT) is known to be markedly elevated when animals are exposed to the cold, and intensive studies have been carried out to understand the molecular basis enabling effective thermogenesis in cold-exposed animals. In this study, we used microarray analysis to examine the effects of cold exposure of animals on their gene expression profiles in white adipose tissue (WAT), which seems to function as a counterpart tissue of BAT. The results indicate that the effects of cold exposure on the gene expression profiles of WAT were much more moderate than the effects on those of BAT. Possible reasons for the different responses of BAT and WAT to cold exposure are discussed.     

Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

A combined effective fragment potential-fragment molecular orbital method. II. Analytic gradient and application to the geometry optimization of solvated tetraglycine and chignolin

The gradient for the fragment molecular orbital (FMO) method interfaced with effective fragment potentials (EFP), denoted by FMO∕EFP, was developed and applied to polypeptides solvated in water. The structures of neutral and zwitterionic tetraglycine immersed in water layers of 2.0, 2.5, 3.0, 3.5, 4.0, and 4.5 A? are investigated by performing FMO∕EFP geometry optimizations at the RHF∕cc-pVDZ level of theory for the solutes. The geometries optimized with FMO-RHF∕EFP are compared to those from the conventional RHF∕EFP and are found to be in very close agreement. Using the optimized geometries, the stability of the hydrated zwitterionic and neutral structures is discussed structurally and in terms of energetics at the second-order M?ller-Plesset theory (MP2)∕cc-pVDZ level. To demonstrate the potential of the method for proteins, the geometry of hydrated chignolin (protein data bank ID: 1UAO) was optimized, and the importance of the inclusion of water was examined by comparing the solvated and gas phase structures of chignolin with the experimental NMR structure.     

Experimental evaluation and constitutive modeling of non-proportional deformation for asymmetric steels

Recently non-proportional deformation has received increased attention from researchers working in the area of experimental and computational modeling of metal deformation. However, most of them are numerical in nature with limited experimental data available, making it further difficult to model non-proportional deformation. In the present work, two-stage uniaxial tests, along with uniaxial cyclic and biaxial tests for different stress ratios, have been performed to evaluate deformation behavior of ultra-low carbon high strength automotive steel. Behaviors like cross-effect and hardening stagnation, which are attributed to the evolution of complex dislocation structures, were observed in this steel. It was also noticed that this steel exhibits tension-compression asymmetry. As for constitutive modeling, a modified asymmetric yield function is proposed to be used with a combined isotropic-kinematic hardening model. Also methods to account for the hardening stagnation during reverse loading and the cross-effect during two-stage deformation are proposed. The resulting constitutive model showed reasonably good agreement with experimental results.     

Mössbauer Spectra of FePS3-Cobaltocene Intercalation Compound

Abstract

Mössbauer spectra of the FePS₃-cobaltocene intercalation compound were measured in the temperature range of 300K to 10K. The spectra, distinct from those of pure FePS₃, suggest the charge transfer from cobaltocene to Fe-S antibonding orbitals of the FePS₃ host lattice.     

Copper(II) chloride as a new,efficient additive suppressing racemization in peptide synthesis by the carbodiimide method

Copper(II) chloride was found to be an extremely efficient additive suppressing racemization in the carbodiimide mediated couplings.     

Radical formation during tensile deformation of highly drawn crystalline poly[p-(2-hydroxyethoxy)benzoic acid] fibers

The micromechanism of tensile deformation of poly[p-(2-hydroxyethoxy)benzoic acid] fibers is discussed on the basis of a detailed esr study of radical formation. The concentration of primary phenoxy radicals, which were detected during deformation at room temperature as a direct indicator of main-chain rupture, was determined by extrapolating the radical decay curves at various strains to zero time. The relation between the initial radical concentration and the strain is well expressed by the cumulative normal distribution curve. By use of this relation and a model of fiber structure, the distribution of the contour length of tie chains was determined. No radicals were detected during a second stretching cycle until the maximum strain in the first run was exceeded. The deformation model which includes alternating crystalline and amorphous regions connected by tie chains, a distribution of contour lengths of tie chains, and a phase transformation of molecular chains in the crystalline region accounted fairly well for the observed stress–strain behavior of monofilaments in first and second stretching cycles. The comparison between the observed and the calculated radical concentration suggests that statistical factors and other deformation mechanisms have to be taken into account.