Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Hydrogen production through dry reforming of biogas using a porous electrochemical cell: Effects of a cobalt catalyst in the electrode and mixing of air with biogas

This paper reports the performance of porous Gd-doped ceria (GDC) electrochemical cells with Co metal in both electrodes (cell No. 1) and with Ni metal in the cathode and Co metal in the anode (cell No. 2) for CO₂ decomposition, CH₄ decomposition, and the dry reforming reaction of a biogas with CO₂ gas (CH₄ + CO₂ → 2H₂ + 2CO) or with O₂ gas in air (3CH₄ +?1.875CO₂ +?1.314O₂ → 6H₂ +?4.875CO +?0.7515O₂). GDC cell No. 1 produced H₂ gas at formation rates of 0.055 and 0.33?mL-H₂/(min?m²-electrode) per 1?mL-supplied gas/(min?m²-electrode) at 600?°C and 800?°C, respectively, by the reforming of the biogas with CO₂ gas. Similarly, cell No. 2 produced H₂ gas at formation rates of 0.40?mL-H₂/(min?m²) per 1?mL-supplied gas/(min?m²) at 800?°C from a mixture of biogas and CO₂ gas. The dry reforming of a real biogas with CO₂ or O₂ gas at 800?°C proceeded thermodynamically over the Co or Ni metal catalyst in the cathode of the porous GDC cell. Faraday's law controlled the dry reforming rate of the biogas at 600?°C in cell No. 2. This paper also clarifies the influence of carbon deposition, which originates from CH₄ pyrolysis (CH₄ → C + 2H₂) and disproportionation of CO gas (2CO → C + CO₂), on the cell performance during dry reforming. The dry reforming of a biogas with O₂ molecules from air exhibits high durability because of the oxidation of the deposited carbon by supplied air.     

Phase behavior in liquid crystallization for diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components

Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.     

DETERMINATION OF PALAEOSTRESSES FROM MESOSCALE SHEAR FRACTURES IN CORE SAMPLES USING THE MULTI-INVERSE METHOD

Palaeostress reconstruction is the key to quantitative characterization of fractured hydrocarbon reservoirs. In order to calculate the palaeostresses responsible for fault activity, faults in oriented core samples can be analysed and the optimal stresses can then be determined from fault-slip data in a least-squares sense. Many fractured reservoir rocks, however, include faults generated during a number of different tectonic phases. In these cases, the optimal stresses can be determined for subgroups of faults which are considered to be of approximately the same age. The difficulty with this is that criteria for accurate age-dating are often absent, especially from core samples.
Recently, the so-called "multi-inverse" method has been proposed to address this problem. This is a numerical technique for separating palaeostresses within a heterogeneous fault assemblage in the absence of a priori information on the faults'relative ages. In this paper, we apply the method to eighteen faults in two short (9m) cores from an exploration well in Hokkaido, northern Japan. The cores came from a fractured hydrocarbon reservoir and were oriented by correlation with borehole images. Core lithologies included massive Cretaceous basalts in which there was no layering which would show fault offsets; for these samples, we determined the sense of shear by studying asymmetric microstructures on the fault surfaces. The results show that the rocks have experienced six different stress regimes. In general, these are compatible with the tectonic history of the study area as inferred from the regional stratigraphy and from macroscale geological structures.
These results show that the multi-inverse method can be used to extract palaeostress data from cores, thereby providing information which will assist with the exploration of (and production from) fractured hydrocarbon reservoirs.     

Changes in cerebral blood flow and oxygen metabolism related to magnetic resonance imaging white matter hyperintensities in Alzheimer's disease

We studied changes in cerebral perfusion and oxygen metabolism to elucidate the pathophysiological nature and clinical significance of white matter hyperintensities in Alzheimer's disease (AD). METHODS: Sixteen AD patients (age 71.6 +/- 3.1 yr) whose T2-weighted MR images showed white matter hyperintensities, and 16 age-matched AD patients (age 71.0 +/- 4.3 yr) without white matter hyperintensities were compared. Regional cerebral blood flow (CBF), oxygen metabolism (CMRO2) and oxygen extraction fraction (OEF) were measured by using (15)O steady-state method and PET. RESULTS: There was no significant difference in cognitive impairment between the two groups. Compared to the patients without white matter hyperintensities, those with them had significantly low CBF values and significantly high OEF values in all cortical and white matter regions. However, there were no significant differences in CMRO2 values between the two groups. Severity of white matter hyperintensities correlated with the mean cortical and mean white matter OEF. CONCLUSION: In AD patients, white matter hyperintensities on T2-weighted MR images represent ischemic changes in which oxygen metabolism and function are fairly compensated. These changes are not disease-specific but are age-associated coincidences, as in normal aging with or without vascular risk factors.     

Construction of a control system for disturbance rejection using a dual observer

A well‐known control system which can reduce the adverse effects of disturbances is a disturbance observer. However, in many cases of mechanical systems, system disturbances which do not satisfy the matching condition may be imposed. Therefore, it may be difficult to reduce the adverse effects of the disturbances by the traditional disturbance observer. In this paper, a method of control system synthesis for disturbance rejection using a dual observer is proposed. This method is based on the zeroing induced by the disturbance localization problem. This problem may be solved by dividing the state space into observable subspace and unobservable subspace. As compared with an H_∞ controller based on perfect observation, the usefulness of the proposed control system for disturbance rejection is demonstrated by numerical simulations for a two‐mass spring system. © 2002 Scripta Technica, Electr Eng Jpn, 138(4): 50–60, 2002; DOI 10.1002/eej.1138     

Intelligent manipulator system with nonsymmetric and redundant master-slave

Some work is so complicated and unsteady that it is not possible to use automatic robots, such as FA robots. In such a case, a teleoperated manipulation system is applied. In this research, the authors aim at a reduction in the operator's physical and mental burdens. An artificially intelligent manipulator system has been developed with nonsymmetric and redundant master-slave. This system has five features: (1) a polar coordinates master arm; (2) a highly operational articulated slave arm with 7 degrees of freedom; (3) a nonsymmetric configuration and different degrees of freedom master-slave control; (4) an expert system; and (5) a new master-slave control motion, which makes the operator's task easier with automatic force/position control. The system was experimentally produced and its performance tested and evaluated. A qualitative evaluation was carried out by conducting a comparative test on the conventional master-slave control and the new master-slave control. It was found to be effective in reducing operating time, as well as work-induced fatigue.     

Theory of rough surface effects on the anisotropic BCS states

We present a Green's function theory of the rough surface effects on the anisotropic BCS states using the formulation developed in the randomly rippled wall model. It is shown that the randomly rippled wall formulation is general enough to treat rough surface effects from the specular limit to the diffusive limit. We propose a statistical wall configuration such that gives the diffusive limit in the normal state. Within the weak coupling theory, we give a formal solution of the quasi-classical Green's function in a slab geometry and in a semi-infinite geometry with arbitrarily rough surfaces. The formal solution already satisfies the boundary condition. In the diffusive limit, the present theory correctly recovers the linearized gap equation obtained by Kjäldman et al. for the p-wave state in a slab geometry.     

X-ray Photoelectron Spectroscopy Investigation on the Low-Temperature Degradation of 2 mol% Y2O3-ZrO2 Ceramics

2 mol% Y₂O₃-ZrO₂ polycrystals were annealed in water and under vacuum to highlight the effect of the presence of H₂O on the low-temperature degradation transformation. The specimen surfaces with monoclinic phases transformed during annealing in the different environments were analyzed by X-ray photoelectron spectroscopy with special interest on the electron binding energy change of the constituent ions of the 2 mol% Y₂O₃-ZrO₂ ceramics after the degradation transformation. It was found that no change occurred for the electron-bonding energies of core levels of zirconium ions after the transformation, whereas Y-OH bonds were formed during annealing in water. This result suggested a possibility that the preferred hydration of yttrium took place at the surface of Y₂O₃-partially-stabilized ZrO₂, which is likely to be the reason for the low-temperature degradation accelerated by the presence of H₂O.     

Identification of SYS1 as a Host Factor Required for Shiga Toxin-Mediated Cytotoxicity in Vero Cells

Shiga toxin (STx) or Vero toxin is a virulence factor produced by enterohemorrhagic Escherichia coli. The toxin binds to the glycosphingolipid globotriaosylceramide (Gb3) for its entry, and causes cell death by inhibiting ribosome function. Previously, we performed a loss-of-function screen in HeLa cells using a human CRISPR knockout (KO) library and identified various host genes required for STx-induced cell death. To determine whether this library targeted to the human genome is applicable to non-human primate cells and to identify previously unrecognized factors crucial for STx-induced cell death, we herein performed a similar screen in the African green monkey kidney-derived Vero C1008 subline. Many genes relevant to metabolic enzymes and membrane trafficking were enriched, although the number of enriched genes was less than that obtained in the screening for HeLa cells. Of note, several genes that had not been enriched in the previous screening were enriched: one of these genes was SYS1, which encodes a multi-spanning membrane protein in the Golgi apparatus. In SYS1 KO Vero cells, expression of Gb3 and sphingomyelin was decreased, while that of glucosylceramide and lactosylceramide was increased. In addition, loss of SYS1 inhibited the biosynthesis of protein glycans, deformed the Golgi apparatus, and perturbed the localization of trans-Golgi network protein (TGN) 46. These results indicate that the human CRISPR KO library is applicable to Vero cell lines, and SYS1 has a widespread effect on glycan biosynthesis via regulation of intra-Golgi and endosome–TGN retrograde transports.