Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

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.     

An improved process of separation of R- and S-timolol

Diastereomeric timolol tartrates 4 are obtained in a one-pot synthesis from the racemic base 2 and optically active O,O-diacetyl- or O,O-dibenzoyltartaric anhydrides 3 , as only one of the diastereomers precipitates from acetone solution. Acidic hydrolysis as the corresponding 4 leads to timolol in high yield and optical purity.     

WIDE RANGE DETECTOR USING PARABOLIC CYLINDRICAL MIRROR FOR THz APPLICATIONS

A new, wide-band, high-speed and high-sensitivity THz detector has been developed. The prototype detector consists of a parabolic cylindrical mirror, a long wire antenna and a Schottky barrier diode. Direct detection measurements have shown a stable sensitivity of 150 ± 50 V/W for 1–2 THz without any adjustments. The long wire antenna was fixed at the focus of parabolic cylindrical mirror then it has been realized less operation steps, easy coupling to the external THz signals and a dramatic enhancement in the practicality of this system. The optically polished mirror and frosted surface one showed comparable sensitivities, thus easy polishing and less cost mirror fabrication can be applied for this system. The radiation pattern showed a maximum radiation angle of approximately 23° with its dominant main lobe, which was attributed to the wire antenna character and confirmed good agreements with classical antenna theory.     

Semi-classical limit of the bottom of spectrum of a Schrödinger operator on a path space over a compact Riemannian manifold

We determine the limit of the bottom of spectrum of Schrödinger operators with variable coefficients on Wiener spaces and path spaces over finite-dimensional compact Riemannian manifolds in the semi-classical limit. These are extensions of the results in [S. Aida, Semiclassical limit of the lowest eigenvalue of a Schrödinger operator on a Wiener space, J. Funct. Anal. 203 (2) (2003) 401-424]. The problem on path spaces over Riemannian manifolds is considered as a problem on Wiener spaces by using Ito's map. However the coefficient operator is not a bounded linear operator and the dependence on the path is not continuous in the uniform convergence topology if the Riemannian curvature tensor on the underling manifold is not equal to 0. The difficulties are solved by using unitary transformations of the Schrödinger operators by approximate ground state functions and estimates in the rough path analysis.     

Intramolecular photoreactions of 6-(ω-alkenyl)-4-methoxy-2-pyrones

6-(ω-Alkenyl)-2-pyrones 3a-c and 8a, b were prepared and the photochemical reactions were investigated. Photosensitized reactions of 3b, c gave intramolecular [2+2]-cycloadducts 11b, c as tricyclic lactones, site-and regio-specifically. They are not frontier-orbital-controlled adducts. On the other hand, 3a, 8a, b afforded cyclobutenecarboxylic acids, 10a, 14a, b , respectively. The end-ester group at the side-chain is thought not to be effective for the intramolecular phptoaddition.     

First thermally responsive supramolecular polymer based on glycosylated amino acid

In materials science, a dynamic property sensitive to an environmental change (heat, light, electric current, pH, and other chemical or physical changes) is indispensable for intelligent materials. Such organic materials, however, are very limited even in conventional polymers. This paper clearly demonstrates that, regardless of the low molecular weight, a glycosylated amino acid derivative newly screened by a combinatorial method forms a macroscopic supramolecular hydrogel that reversibly swells or shrinks in response to the external temperature. Using the unique thermal response of the present hydrogel, we carried out the controlled release of DNA and the perfect removal of bisphenol A from the polluted water. Recently, advanced supramolecular polymers, in which monomers are noncovalently connected, are expected to be highly advantageous over traditional polymers because of their tunable and recyclable characteristics. The present result newly confers a dynamic feature on the supramolecular polymers, which is desirable for the sophisticated application in many fields.     

Measurement of acid-catalyzed isomerization of unsaturated aldehyde-2,4-dinitrophenylhydrazone derivatives by high-performance liquid chromatography analysis

Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers.