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.     

Wide-band polarization-independent tensile-strained InGaAs MQW-SOAgate

A high-performance tensile-strained InGaAs multi-quantum-well semiconductor optical amplifier (MQW-SOA) gate developed for wavelength-division-multiplexing (WDM) applications is reported. The -0.47% InGaAs-strained SOA gate has a very low polarization dependence of 0.3 dB over a driving current between 30 and 60 mA and a wide-input signal wavelength range from 1530 to 1580 nm. The fabrication tolerance of the mesa stripe width is very large, ranging from 1.0 to 1.75 μm. The MQW-SOA gate has an extinction ratio of more than 40 dB. The fiber-to-fiber lossless operation current is less than 50 mA over the fiber-amplifier gain band. The gating speed is less than 1 ns     

Data fitting with a spline using a real-coded genetic algorithm

To obtain a good approximation for data fitting with a spline, frequently we have to deal with knots as variables. The problem to be solved then becomes a continuous nonlinear and multivariate optimization problem with many local optima. Therefore, it is difficult to obtain the global optimum. In this paper, we propose a method for solving this problem by using a real-coded genetic algorithm. Our method can treat not only data with a smooth underlying function, but also data with an underlying function having discontinuous points and/or cusps. We search for the best model among candidate models by using the Bayes Information Criterion (BIC). With this, we can appropriately determine the number and locations of knots automatically and simultaneously. Five examples of data fitting are given to show the performance of our method.     

Subarachnoid haemorrhage induced proliferation of leptomeningeal cells and deposition of extracellular matrices in the arachnoid granulations and subarachnoid space. Immunhistochemical study

Subarachnoid haemorrhage (SAH) often leads to subarachnoid fibrosis and resultant normal pressure hydrocephalus; however, how subarachnoid fibrosis occurs is unknown. We examined the changes within arachnoid granulations (AGs) and the subarachnoid space (SAS) chronologically at the parasagittal region obtained from patients with SAH at autopsy and made comparison with controls by immunostaining for cytokeratin, specific marker for leptomeningeal cells and by the elastica Masson-Goldner methods. Within a week some AGs were torn, and many inflammatory cells filled the AGs and SAS. Cytokeratin positive cells were scarce. During the next two weeks cytokeratin positive cells increased. After three weeks, AGs and SAS were filled by dense deposits of extracellular matrices surrounded by multiple layers of leptomeningeal cells.     

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     

Distribution of total uptime during a given time interval

The distribution of total uptime during a given time interval for a repairable system is obtained. The total uptime is the total amount of time the system is up (in operation) during the interval. It is assumed that: (1) the system starts to operate at the beginning of the interval and alternately takes only the two states, up and down (under repair); (2) repair restores the system to “like-new”. A simple approximation to the distribution function of total uptime for a shorter interval is presented     

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.