Coordination‐Induced Spin‐State Switching of an Aminyl‐Radical‐Bridged Nickel(II) Porphyrin Dimer between Doublet and Sextet States

A bis(Ni^II‐porphyrinyl)aminyl radical with meso‐C₆F₅ groups was prepared as a spin‐delocalized stable aminyl radical with a doublet spin state. Upon addition of pyridine, both Ni^II centers became hexacoordinated by accepting two axial pyridines, which triggered a spin‐state change of the Ni^II centers from diamagnetic (S=0) to paramagnetic (S=1). The resulting high‐spin Ni^II centers interact with the aminyl radical ferromagnetically to give rise to an overall sextet state (S=5/2). Importantly, this coordination‐induced spin‐state switching can be conducted in a reversible manner, in that washing of the high‐spin radical with aqueous hydrochloric acid regenerates the original doublet radical in good yield.     

Atomic-scale visualization of antisite defects in LiFePO4

We visualize the antisite exchange defects in LiFePO4 crystals with an ordered olivine structure by using annular dark-field scanning transmission electron microscopy (STEM). A recognizable bright contrast is observed in some of the Li columns of STEM images in a sample annealed at a lower temperature, which directly demonstrates the disordered occupations by Fe atoms. Furthermore, such exchange defects appear to be locally aggregated rather than homogeneously dispersed in the lattice, although their overall concentration is fairly low. The present study emphasizes the significance of atomic-level observations for the defect distribution that cannot be predicted by macroscopic analytical methods.     

Topological aspects of excitons in artificial structure

The exciton properties of thin nanotube structures are investigated theoretically. Anisotropic size dependencies have been found in the exciton binding energy, the kinetic energy for the relative motions of an electron and a hole, and the wavefunction. These anisotropies arise from the different boundary conditions in the tube-length and circumferential directions, namely, the topological features of nanotubes. We also found that it is possible to change the topology of exciton wavefunctions by varying the tube-length and the tube-radius. These findings suggest that the optical properties of nanotubes such as oscillator strength or nonlinear susceptibilities can be controlled by tuning the structural parameters, thus yielding a novel guiding principle for designing optical functional materials.     

Removal and regeneration of aqueous divalent cations by boehmite

Boehmite (Al(OH)O) was employed for the removal of aqueous Mg(2+), Cu(2+), Cd(2+), Pb(2+), and Co(2+) at 298 K. Although boehmite was able to remove these divalent cations, the greater removal rate with boehmite of Pb(2+) (28.7%) than with Mg(2+), Cu(2+), Cd(2+), and Co(2+) (5.6, 25.3, 10.9, and 13.3%, respectively) was observed under acidic conditions. Under stronger alkaline conditions, in which the lead species was completely dissolved, a greater removal rate of Pb(2+) (more than 80%) was observed under the corresponding conditions employed for the acidic conditions. The removed lead species could not be dissolved from boehmite in an acidic solution while an evident dissolution of lead species was detected using an aqueous NaOH solution. The results shown in the present study reveal that boehmite can be employed as a reagent for the removal and regeneration of aqueous metal cations.     

Sequential stir bar sorptive extraction for uniform enrichment of trace amounts of organic pollutants in water samples

A novel extraction procedure for stir bar sorptive extraction (SBSE) termed sequential SBSE was developed. Compared to conventional SBSE, sequential SBSE provides more uniform enrichment over the entire polarity/volatility range for organic pollutants at ultra-trace levels in water. Sequential SBSE consists of a SBSE performed sequentially on a 5-mL sample first without modifier using one stir bar, then on the same sample after addition of 30% NaCl using a second stir bar. The first extraction with unmodified sample is mainly targeting solutes with high Kow (logKow>4.0), the second extraction with modified sample solution (containing 30% NaCl) is targeting solutes with low and medium Kow (logKow<4.0). After extraction the two stir bars are placed in a single glass desorption liner and are simultaneously desorbed. The desorbed compounds were analyzed by thermal desorption and gas chromatography-mass spectrometry (TD-GC-MS). Recovery of model compounds consisting of 80 pesticides (organochlorine, carbamate, organophosphorus, pyrethroid, and others) for sequential SBSE was evaluated as a function of logKow (1.70-8.35). The recovery using sequential SBSE was compared with those of conventional SBSE with or without salt addition (30% NaCl). The sequential approach provided very good recovery in the range of 82-113% for most of the solutes, and recovery less than 80% for only five solutes with low Kow (logKow<2.5), while conventional approaches (with or without salt addition) showed less than 80% recovery for 23 and 41 solutes, respectively. The method showed good linearity (r2>0.9900) and high sensitivity (limit of detection: <10ngL(-1)) for most of the model compounds even with the scan mode in the MS. The method was successfully applied to screening of pesticides at ngL(-1) level in river water samples.     

Energy-saving drying technology for porous media using liquefied DME gas

Process design and energy requirement for a practical plant are investigated for an energy-saving drying (dewatering) process invented by the authors in 2002 for high-moisture porous materials. The basic concept of the process involves the extraction of water from a high-moisture porous material by bringing it in physical contact with liquefied dimethyl ether (DME) at room temperature. Water content of DME asymptotically increases to the saturation value and the high-moisture porous material is dried almost perfectly. DME from the DME-water mixture is vaporized by decompression. DME and water are separated by flash distillation. DME vapor is compressed and cooled in a heat exchanger, and the latent heat of condensation is reused to vaporize the DME in the heat exchanger. Multistage compression and multistage flash distillation are employed. After compression, the temperature of DME is less than 50?°C. Because specific heat ratio of DME is only 1.11, the energy consumption of the compressor is reduced. Considering the adiabatic efficiency of the compressor and the net thermal efficiency, the total energy for dewatering is about 1100 kJ per 1-kg-water-content of the material being dewatered This process has significant potential and is compact than the existing dewatering processes.     

Spontaneous vesicle formation of single chain and double chain cationic surfactant mixtures

The concentration vs composition diagram of aggregate formation of the dodecyltrimethylammonium bromide (DTAB) and didodecyldimethylammonium bromide (DDAB) mixture in aqueous solution at rather dilute region was constructed by analyzing the surface tension, turbidity, and electrical conductivity data and inspected by cryo-TEM images and dynamic light scattering data. Although the aqueous solution of DTAB forms only micelles, the transition from monomer to small aggregates and then to vesicle was found at 0.1 < X2 相似文献   

Modulation of the absorption maximum of rhodopsin by amino acids in the C-terminus

Vision begins when light is absorbed by visual pigments. It is commonly believed that the absorption spectra of visual pigments are modulated by interactions between the retinal and amino acids within or near 4.5 angstroms of the retinal in the transmembrane (TM) segments. However, this dogma has not been rigorously tested. In this study, we show that the retinal-opsin interactions extend well beyond the retinal binding pocket. We found that, although it is positioned outside of TM segments, the C-terminus of the rhodopsin in the rockfish longspine thornyhead (Sebastolobus altivelis) modulates its lambda(max) by interacting mainly with the last TM segment. Our results illustrate how amino acids in the C-terminus are likely to interact with the retinal. We anticipate our analyses to be a starting point for viewing the spectral tuning of visual pigments as interactions between the retinal and key amino acids that are distributed throughout the entire pigment.     

Growth Curve Model with Hierarchical Within-Individuals Design Matrices

This paper deals with some inferential problems under an extended growth curve model with several hierarchical within-individuals design matrices. The model includes the one whose mean structure consists of polynomial growth curves with different degrees. First we consider the case when the covariance matrix is unknown positive definite. We derive a LR test for examining the hierarchical structure for within individuals design matrices and a model selection criterion. Next we consider the case when a random coefficients covariance structure is assumed, under certain assumption of between-individual design matrices. Similar inferential problems are also considered. The dental measurement data (see, e.g., Potthoff and Roy (1964, Biometrika, 51, 313-326)) is reexamined, based on extended growth curve models.     

In situ observation of protein-adsorbed stearic acid monolayer by Brewster angle microscopy and fluorescence microscopy

A fluorescence probe, fluorescein isothiocyanate (FITC), was introduced to proteins, and the morphology of protein-adsorbed stearic acid monolayer was observed by fluorescence microscopy and Brewster angle microscopy (BAM) in order to analyze images. At a low protein concentration, the surface pressure increased as shown by a sigmoidal curve. A number of stripe patterns in the BAM images increased and the shapes became clear with increasing concentration of proteins. Simultaneously, the size of circular islands also became small, and finally disappeared. These results suggest that the very large stripe patterns in the BAM image show the assembly of both proteins and stearic acid molecules, and small circular islands show only the stearic acid molecules. © 1998 John Wiley & Sons, Ltd.