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.     

Analysis of course errors on CVOR antennas (including effects ofmutual coupling between elements)

A VHF omnidirectional radio range (VOR) is a navigation aid radio beacon facility, which provides aircraft with azimuth information relative to the VOR station in question as the origin. In Japan, two types of VOR-the conventional type (referred to as a CVOR) and the Doppler type (referred to as a DVOR)-are currently in use. An element known as the Alford loop antenna (ALA), which changes the loading reactance, is used for the VOR because the horizontally polarized wave and nondirectivity in the horizontal plane are preferred. A VOR antenna consists of a carrier antenna and a sideband antenna-an aircraft receives separate signals from these two antennas and compares them to obtain azimuth information. The mutual coupling between the elements forming the carrier and the sideband antenna affects the directivity of the single elements, resulting in errors in azimuth information. With the mutual coupling between the antenna elements being taken into consideration, a quantitative calculation was made by using the moment method-the results of the calculation made it clear that a loading reactance value of -320 Ω is better to make not mutually coupled elements nondirectional while a loading reactance value of -600 Ω is optimum to minimize the azimuth error of a CVOR     

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     

Sub-50-nm physical gate length CMOS technology and beyond usingsteep halo

Sub-50-nm CMOS devices are investigated using steep halo and shallow source/drain extensions. By using a high-ramp-rate spike annealing (HRR-SA) process and high-dose halo, 45-nm CMOS devices are fabricated with drive currents of 650 and 300 μA/μm for an off current of less than 10 nA/μm at 1.2 V with T_ox^inv =2.5 nm. For an off current less than 300 nA/μm, 33-nm pMOSFETs have a high drive current of 400 uA/μm. Short-channel effect and reverse short-channel effect are suppressed simultaneously by using the HRR-SA process to activate a source/drain extension (SDE) after forming a deep source/drain (S/D). This process sequence is defined as a reverse-order S/D (R-S/D) formation. By using this formation, 24-nm nMOSFETs are achieved with a high drive current of 800 μA/μm for an off current of less than 300 μA/μm at 1.2 V. This high drive current might be a result of a steep halo structure reducing the spreading resistance of source/drain extensions     

Preparation of Copper-Ruby Glasses by Sputtering: The Effect of Atmosphere on the Growth of Copper Particles

Copper-ruby glasses were prepared by the sputtering method and the effect of reducing treatment was examined. The reducing was carried out either during sputtering or heat treatment. Optical absorption was related to the growth of copper particles. The results are summarized as follows: (i) the volume fraction of copper particles in the glasses which are heat-treated in air increases with the addition of hydrogen in the sputtering gas. (ii) The copper particles do not grow larger than 8 nm by heat treatment in reducing atmosphere, whereas they grow as large as 12 nm in air. (iii) Reducing during heat treatment gives a pronounced effect only when sputtering was not carried out under reducing conditions. The origin of these phenomena was also discussed, considering the mechanism of nucleation and growth of copper particles.     

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.     

Polarimetric Characteristics of sea ice in the sea of Okhotsk observed by airborne L-band SAR

The Phased-Array L-Band SAR (PALSAR) aboard the Advanced Land Observing Satellite (ALOS) is capable of globally acquiring fully polarimetric data. In order to confirm the ability of L-band polarimetric synthetic aperture radar (SAR) to investigate sea ice before the ALOS launch, we conducted a field experiment using an airborne Polarimetric and Interferometric SAR (Pi-SAR) in the Sea of Okhotsk in 1999. This paper presents the analyzed results of data acquired in that experiment. The extracted polarimetric parameters of several ice types suggested that polarimetric coherences and phase differences between right-right (RR) and left-left (LL) are good candidates for discriminating ice types. The polarimetric anisotropy as well as the beta angle of the first eigenvector calculated in the polarimetric decomposition procedure are alternative parameters that are sensitive to ice type differences. Due to the low depolarization characteristics of open water, it could be discriminated from sea ice by scattering entropy in all incidence angle ranges. From the relation between ice thickness and the polarimetric parameters, we found that backscattering coefficients and vertical (VV) to horizontal (HH) backscattering ratio are highly correlated with ice thickness. Since the ratio is sensitive to ice surface dielectric constants, a simple simulation using the integral equation method surface model was conducted by using the physical parameters of typical sea ice. A two-dimensional ice thickness map was derived from an empirical relation between the VV-to-HH backscattering ratio and ice thickness.