Measurement of circular dichroism spectra of liquid/liquid interface by centrifugal liquid membrane method.

The direct measurement of the circular dichroism (CD) spectra of liquid/liquid interface has been achieved for the first time by the centrifugal liquid membrane (CLM) method combined with a conventional CD spectropolarimetry. In the sample chamber of the CD spectropolarimeter, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at ca. 7000 rpm to generate a two-phase liquid membrane with a high specific interfacial area. The CD spectra of the J-aggregate of protonated 5,10,15,20-tetraphenylporphyrin formed at the toluene/sulfuric acid interface in the rotating cell have been measured. The results demonstrated the novelty and advantages of this method.     

Surface-enhanced Raman scattering from oleate-stabilized silver colloids at a liquid/liquid interface.

Oleate-stabilized silver colloids of 5-nm-diameter were adsorbed to a toluene/water interface, and surface enhanced Raman scattering (SERS) spectra from these colloids were measured under the total internal reflection (TIR) condition. From the observed spectra, we examined the states of oleate ions and toluene molecules on silver colloids at the liquid/liquid interfacial region. The TIR-SERS spectra of oleate ions showed stronger peaks of the carboxylate group and the ethylene group than those of alkyl chains. From these results, it was found that the oleate ions were adsorbed on the silver surface in two different ways at the liquid/liquid interface; the carboxylate group adsorbed in the organic phase side, while the ethylene group adsorbed in the aqueous phase side. The shifts of the toluene in the interfacial SERS spectra were identical to those of bulk toluene, though the relative intensities among the peaks were not same. This result suggested that the toluene was adsorbed with a weak interaction, but was significantly enhanced by the local electromagnetic field at the colloid surface.     

Synthesis and characterization of crosslinked uniform polymeric microspheres containing a polyimide prepolymer by a new emulsification process

A highly crosslinked poly(styrene–divinyl benzene–trimethyolpropane trimethacrylate) microsphere containing a polyimide prepolymer (PIP) was prepared by a new emulsification method, Shirasu porous glass (SPG) membrane emulsification, and a subsequent radical suspension polymerization. That is, a mixture of styrene, divinyl benzene, trimethyol propane trimethacrylate (TMPTMA), and PIP containing an initiator was permeated through the uniform pores of the SPG membrane into a continuous phase containing a stabilizer to form uniform droplets. Then, the suspension polymerization was carried out at 65 °C for 24 h. The trifunctional crosslinker TMPTMA was added to enhance the destructive strength of the microsphere, and PIP was incorporated into the microsphere to provide an adhesion force by a known self‐curing reaction at 220 °C. The effects of the feed amounts of TMPTMA and PIP on the monomer conversion, size distribution, and destructive strength of the microsphere were investigated. The monomer conversion increased with an increase in TMPTMA. The particle size distribution became narrower as the TMPTMA feed amount increased, but it became broader with an increase in PIP. The destructive strength increased with increases in TMPTMA and PIP. After a heat treatment at 220 °C, the destructive strength decreased because of the heat degradation of the polymer. The addition of TMPTMA suppressed the heat degradation, and PIP could undergo self‐curing at 220 °C. The obtained highly crosslinked uniform microsphere containing PIP has potential applications in liquid‐crystal displays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2588–2598, 2003     

Performance of noise barriers with various edge shapes and acoustical conditions

The performances of barriers having different shapes and surface conditions were tested using the boundary element method in a well-controlled environment. The heights and widths of the barriers were standardized and the insertion losses for six receiver positions were averaged and compared. Figures displaying the results allow for straightforward barrier performance estimation. It was shown that absorbing and soft edges significantly improve the efficiency of the barrier, but configuration modifications provide only a slight improvement. The soft T-shaped barrier produces the highest performance. A 3 m high T-shaped barrier provides the same performance as a 10 m high plain barrier. The spectral efficiency was also investigated. The insertion loss spectra for the absorbing and the soft barriers exhibit a similar shape, but the rigid barrier differs from these two.     

Growth of SiGe bulk crystals with uniform composition by utilizing feedback control system of the crystal–melt interface position for precise control of the growth temperature

We developed an automatic feedback control system of the crystal–melt interface position to keep the temperature at the interface constant during growth, and demonstrate its successful application to grow Ge-rich SiGe bulk crystals with uniform composition. In this system, the position of the crystal–melt interface was automatically detected by analyzing the images captured using in situ monitoring system based on charge-coupled-devices camera, and the pulling rate of the crucible was corrected at every 1 min. The system was found to be effective to keep the crystal–melt interface position during growth even when the variation of the growth rate is quite large. Especially, the interface position was kept for 470 h during growth of Ge-rich SiGe bulk crystal when we started with a long growth melt of 80 mm. As a result, a 23 mm-long Si_0.22Ge_0.78 bulk crystal with uniform composition was obtained thanks to the constancy of the growth temperature during growth through the control of the interface position. Our technique opens a possibility to put multicomponent bulk crystal in a practical use.     

Synthesis and photophysical properties of azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-diones: Azulene analogs of tryptanthrin

Azulene analog of tryptanthrin, azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-dione, was successfully prepared by the condensation reaction of azuleno[2,1-b]pyrrole-2,3-dione with isatoic anhydride in the presence of sodium hydride or diisopropylethylamine (DIPEA). Its 2-halo derivatives were also obtained in high yields by the condensation reaction with 5-haloisatoic anhydrides in the presence of DIPEA. Reactivity toward electrophilic reagents was revealed by halogenation with N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS) to afford 12-halo derivatives in high yields. Among the halo derivatives, 2-iodo and 12-iodo derivatives were reactive enough to afford phenylethynyl derivatives under Pd-catalyzed Sonogashira cross-coupling conditions. Within the phenylethynyl derivatives, only 12-phenylethynyl derivative was transformed into its 1,1,4,4-tetracyanobutadiene (TCBD) derivative by the reaction with TCNE. Amphoteric redox properties of the novel azulene analogs of tryptanthrin were characterized by spectroscopic and voltammetric analyses.     

A new high‐pressure strontium germanate,SrGe2O5

The Sr–Ge–O system has an earth‐scientific importance as a potentially good low‐pressure analog of the Ca–Si–O system, one of the major components in the constituent minerals of the Earth's crust and mantle. However, it is one of the germanate systems that has not yet been fully examined in the phase relations and structural properties. The recent findings that the SrGeO₃ high‐pressure perovskite phase is the first Ge‐based transparent electronic conductor make the Sr–Ge–O system interesting in the field of materials science. In the present study, we have revealed the existence of a new high‐pressure strontium germanate, SrGe₂O₅. Single crystals of this compound crystallized as a co‐existent phase with SrGeO₃ perovskite single crystals in the sample recovered in the compression experiment of SrGeO₃ pseudowollastonite conducted at 6 GPa and 1223 K. The crystal structure consists of germanium–oxygen framework layers stacked along [001], with Sr atoms located at the 12‐coordinated cuboctahedral site; the layers are formed by the corner linkages between GeO₆ octahedra and between GeO₆ octahedra and GeO₄ tetrahedra. The present SrGe₂O₅ is thus isostructural with the high‐pressure phases of SrSi₂O₅ and BaGe₂O₅. Comparison of these three compounds leads to the conclusion that the structural responses of the GeO₆ and GeO₄ polyhedra to cation substitution at the Sr site are much less than that of the SrO₁₂ cuboctahedron to cation substitution at the Ge sites. Such a difference in the structural response is closely related to the bonding nature.     

Ultrafine Metal–Organic Right Square Prism Shaped Nanowires

We report the structural design and control of electronic states of a new series of ultrafine metal–organic right square prism‐shaped nanowires. These nanowires have a very small inner diameter of about 2.0 Å, which is larger than hydrogen and similar to xenon atomic diameters. The electronic states of nanowires can be widely controlled by substitution of structural components. Moreover, the platinum homometallic nanowire shows a 100 times higher proton conductivity than a palladium/platinum heterometallic one depending on the electronic states.     

Inelastic scattering on 12Be and disappearance of the N = 8 magic number

Experimental studies on in-beam γ-ray spectroscopy using a ¹²Be radioactive beam are presented. Inelastic scattering of the neutron-rich ¹²Be nucleus on ²⁰⁸Pb, ¹²C, and (CH₂)_n targets has been studied by measuring de-excitation γ-rays in coincidence with scattered particles. The level schemes and transition probabilities are determined for low-lying excited states in ¹²Be. The present paper presents a brief review of the spectroscopic results, which may be associated with the N = 8 shell quenching near the drip line. Received: 1 May 2001 / Accepted: 4 December 2001