Charge Transfer Transitions from Cyclohexadienyl-Type Radicals to Host Molecules in Anthracene Single Crystals

The optical absorption spectra of 1-, 2- and 9-dibenzo-cyclohexadienyl radical in anthracene crystals have been obtained and analyzed. It is shown that the absorption lines consist of vibrational progression and charge-transfer lines for 2- and 9-DBCR. Each line belonging to the former has the same polarization as the most intense 0–0 vibrational line and the latter show polarization character depending on the direction of charge transfer and the transition energy was found to have a coulombic dependence on the distance of charge transfer. It is pointed out that only charge transfer lines were observed for 1-DBCR. The splitting of lines were observed and ascribed either to the resonance transfer interaction between two neighboring molecules situated at an equal distance from the radical or to the site symmetry. It is suggested that the intensity of the charge-transfer lines are borrowed from the intra-radical transition. The result that the charge transfer lines are more intense than the intra-radical lines for 1-DBCR was discussed.     

Manganese centers with various valency in alkali halides

Abstract

Optical absorption bands and epr spectra of NaCl: Mn⁺⁺ X-irradiated at liquid nitrogen and room temperature are studied. Manganese epr spectra are divided into three classes, based on the value of hyperfme splitting constants. It is shown that the epr spectra with the hyperhe splitting constants of around 250 × 10-⁴, 80 × 10^?4 and 20 × 10^?4 cm^?1 are caused by Mn⁺, Mn⁺⁺ and Mn⁹, respectively. Formation of several manganese centers by X-irradiation is discussed. It is suggested that optical absorption bands at 410 and 440 nm are caused by Mn^O at the lattice site and that the Mn^O center which gives an epr spectrum with A = 15. 5 × 10^?4 cm^?1 is associated with a Mn⁰ center which is not at a substitutional site.     

Stereocontrolled synthesis of 7-hydroxy- and 7-acetoxy-PGI2: New stable PGI2 analogues

Stable analogues of PGI₂, 7-hydroxy- and 7-acetoxy-PGI₂, were synthesized from protected PGI₂ methyl ester $\text{1b}$via sulfoxides $\text{6a}$, $\text{6b}$ through stereocontrolled sulfoxide-sulfenate rearrangement.     

PICOSECOND LASER PHOTOLYSIS STUDIES OF FLUORESCENCE QUENCHING MECHANISMS OF FLAVIN: A DIRECT OBSERVATION OF INDOLE-FLAVIN SINGLET CHARGE TRANSFER STATE FORMATION IN SOLUTIONS and FLAVOENZYMES

Formation of singlet charge transfer (heteroexcimer) states in the course of the fluorescence quenching of lumiflavin and riboflavin tetrabutyrate by indole and N-methylindole have been directly observed by means of time-resolved absorption spectral measurements using a picosecond laser photolysis method. Similar transient spectra have been observed also in the case of a flavoenzyme, D-amino acid oxidase.     

Hue-preserving image enhancement in CIELAB color space considering color gamut

Optical Review - In this paper, we propose a color image enhancement method that uses the CIELAB color space to improve the quality of degraded images for human visual perception. In our method,...     

Gradient-norm-based histogram equalization taking account of HSV color space distribution

In the present paper, we propose an image contrast enhancement method that can enhance the contrast of a color image naturally by taking account of a color space shape. The proposed method realizes the natural enhancement based on two kinds of intensity histograms: a gradient-norm-based histogram and an ideal histogram derived from the shape of a color space. The former histogram is used to suppress over-enhancement in the flat regions of an image and the latter histogram is used to prevent the whole image from being darken. Concretely, the aforementioned intensity histograms are appropriately mixed into a histogram with a weight based on the average intensity of the input image. The contrast enhancement of the input image is realized using the cumulative histogram of the mixed histogram as an intensity transform function. To verify the validity of the proposed method, in experiments, the proposed method is applied to a variety of images and experimental results are evaluated qualitatively and quantitatively.     

Circular dichroism of optically active poly(dialkylsilane) aggregates in microcapsules

Poly[n-hexyl-(S)-3-methylpentylsilane] aggregates confined in microcapsules to keep the aggregation number and ranging in average polymer mass m(p) in a microcapsule from 2 x 10(-)(16) to 2 x 10(-)(14) g were studied by circular dichroism measurements in ethanol (a nonsolvent) and tetrahydrofuran (an associative solvent at low temperature) at various temperatures. The weight-average molecular weight M(w) and the polydispersity index (the ratio of M(w) to the number-average molecular weight) of the polysilane sample were 6.6 x 10(4) and 1.07, respectively, and the average number of polymer molecules in each capsule was estimated to be 1.9 x 10(3) for m(p) = 2 x 10(-)(16) g and 1.7 x 10(5) for m(p) = 2 x 10(-)(14) g. The size of each aggregate did not affect the optical activity because the circular dichroism thus obtained was proportional to m(p) under the same conditions in the investigated m(p) range; on the other hand, the peak height of the circular dichroism in tetrahydrofuran had a significant hysteresis between 0 and 25 degrees C. Moreover, the circular dichroism appreciably reflected the prepared method, that is, the temperature and solvent; in other words, the aggregates memorized the initial conditions in their stacking structures.     

Structure-Chemical Analysis of Multiple Complexations by Cyclodextrins

The interactions between cyclodextrin and substrates having two binding sites in aqueous solution are reviewed. For such substrates, multiple equilibria, NMR chemical shift variations with full binding, solution structures of complexes, and the effect of cavity size are analyzed quantitatively. After general treatments of multiple equilibria and chemical shifts are given, they are applied to three bivalent substrates of diheptanoyllecithin, dialkyldimethylammonium bromide, and oxyphenium bromide for demonstrating their usefulness. The solution structures of complexes play a crucial role in these basic researches as well as the applications of cyclodextrins, such as bitter taste reduction and stabilization of labile substrates.     

Observational Results of Stellar Speckle Interferometric Spectroscopy

Stellar speckle spectroscopy is a speckle interferometric method enabling us to separate point by point spectra on a stellar object with a diffraction-limited spatial resolution of a telescope. We describe observational results obtained with our system for speckle spectroscopy. Data of two binary stars, of which separations are closer than seeing disc, were taken and processed by cross-correlation method. In each object, spectral images of two component stars around the Hα line (656.3 nm) were spatially resolved with nearly diffraction-limited resolution. The separated spectra of ADS940 reveal different spectral types of the component stars. These results demonstrate the ability of the speckle spectroscopic method.Presented at the International Commission of Optics Topical Meeting, Kyoto, 1994.     

Light absorption due to higher harmonics of molecular vibrations in transparent amorphous polymers for plastic optical fibers

We have studied simple empirical equations to estimate light absorption loss α_v due to harmonics of molecular vibrations of transparent amorphous polymers used in plastic optical fibers (POFs). In the visible region, absorption involves two losses. One is α_v, and the other is the electronic transition absorption loss, α_e. Of the two, α_v is considerably larger than α_e in the wavelength region used for optical communication with POFs. We have clarified relationships between chemical structure of repeat units of polymers and α_v. We find that α_v is proportional to the concentration of specific chemical bonds (C? H, N? H, and Obond;H bonds) in the polymer solid, and we propose empirical equations to estimate α_v from the polymer density and the chemical structure of the repeat unit. These equations are used to estimate α_v of several polymers [i.e., poly(methyl methacrylate), polystyrene, and polycarbonate]. The estimated values are nearly equal to the experimental or reference values. Furthermore, to minimize the attenuation in the POF, we conclude that the POF core polymer should have no N? H, O? H, or aliphatic C? H bonds in its repeat unit.