Surface-enhanced Raman scattering from crystal violet adsorbed on a silver electrode

SERS from crystal violet (CV) on a Ag electrode was investigated under preresonance and resonance conditions. The excitation profile of the chemisorbed species is like that of dissolved molecules but intensities are ≈ 1000 times larger. The Raman enhancement is ≈ 10⁸ and exhibits a specific potential dependence even in the absence of adsorption-desorption process. At potentials where reduction of CV occurs leuco crystal violet was detected.     

PHOTORECEPTOR CELL TYPES IN THE RETINA OF VARIOUS VERTEBRATE SPECIES: IMMUNOCYTOCHEMISTRY WITH ANTIBODIES AGAINST RHODOPSIN AND IODOPSIN

Types of photoreceptor cells in the retinas of 36 species of vertebrates (5 classes, 14 orders) were investigated immunocytochemically with monoclonal antibodies against chicken iodopsin (Io-mAb) and antiserum against bovine rhodopsin (Rh-As). In mammals, Rh-As labeled the outer segments of some photoreceptor cells in striped squirrels (a diurnal mammal) and those of most photoreceptor cells in mice (a nocturnal mammal), while Io-mAb labeled any photoreceptor cells in either of them. In all species of birds studied, Io-mAb labeled the principal and accessory members of double cones and single cones with a red oil droplet. Rh-As labeled single cones with a yellow or clear oil droplet in addition to rods. In turtles, both Rh-As and Io-mAb labeled single cones with a red or clear oil droplet and the principal (with a yellow oil droplet) and accessory members of double cones. This suggests that the visual pigments in these cones of turtles have common epitopes with bovine rhodopsin and chicken iodopsin. In Japanese grass lizards, single cones with a yellow oil droplet and double cones were immunoreactive to both Rh-As and Io-mAb. In snakes, rods and cones could not be distinguished but both positively and negatively stained cells were observed by the use of each antibody. In geckos, however, all photoreceptor cells were immunonegative to Io-mAb. In all species studied in amphibians, Rh-As labeled rods but not cones. Neither rods nor cones reacted with Io-mAb. In fishes, almost all species studied had well developed cones, and some of these cones were labeled by Rh-As. However, Io-mAb labeled the outer segments of some cones only in loaches. Rh-As labeled photoreceptor cells in all species of fishes studied. Thus, Rh-As recognized the outer segments of rods in all species studied from fishes to mammals, whereas the epitope recognized by Io-mAb is conserved in some species of fishes, most species of reptiles and all species of birds studied.     

Synthesis and γ-radiolysis of 2′-deoxy-5-fluorouridine and 5-fluorouridine derivatives

Seventeen compounds having a variety of substituents at the 3- and 5′-positions of 2′-deoxy-5-fluorouridine (5-FUdR) and 5-fluorouridine (5-FUR) were synthesized, and their γ-radiolysis in aqueous solutions were studied. The compounds having thioureido (RNHCSNH, R  H, PhCH₂, acyl) and thiocarbonylamino (XCSNH, X  PhCH₂S, PhO) groups at the 3-position of 5-FUdR were efficiently cleaved to give 5-FUdR with high G values upon γ-irradiation of their aqueous solutions. The active species for these cleavage reactions were hydrated electron (e⁻ _aq), H^• and HO^•. However, the compounds having a dimethylsulfoxyimino group at 3-position of 5-FUdR and 5-FUR afforded 5-FUdR and 5-FUR only under the radiolysis conditions where e⁻ _aq becomes a principal active species. The compound having a 2-benzoylthiazoylthiocarbonylamino group at the 3-position of 5-FUdR showed the highest reactivity toward HO^.. The mechanisms of these γ-radiolysis reactions are discussed. The examination of anticellular activities of γ-irradiated compounds having a thiocarbonylamino group at the 3-position of 5-FUdR toward murine Sarcoma 180 cells revealed that these compounds may be utilized as a candidate for a radiation-induced drug (RID).     

A new approach to the synthesis of pyridazino[4,5-c]pyridazinones

The reaction of 5-hydrazinopyridazin-3(2H)-ones 1 with α-keto diester 2 in acetic acid afforded the corresponding 4,6-dihydropyridazino[4,5-c]pyridazin-5(1H)-ones 3 and pyrrolo[2,3-d)pyridazin-4(5H)-ones 4 . Compounds 3 were also obtained from 4-bromo-5-hydrazinopyridazin-3(2H)-ones 8 and 2 under milder conditions. 5-Bromo-4-hydrazinopyridazin-3(2H)-one 9 , the regioisomer of 8b , also reacted readily with 2a to give 4,7-dihydropyridazino[4,5-c]pyridazin-8(1H)-one 10b , the regioisomer of 3b .     

Preparation of dehydrated powder of hemoglobin vesicles

The carbonyl hemoglobin (CO-Hb), which was used to prevent denaturation (metHb) during the preparation of samples, was encapsulated into lipid vesicles constituted from unsaturated phospholipid, cholesterol and unsaturated fatty acid. Unsaturated components were polymerized by γ-irradiation to enhance the stability of bilayer membrane. An aqueous dispersion of resulting Hb vesicles was freeze-dried in the presence of saccharides (50–200 mM) to obtain a dehydrated powder of Hb vesicles. Change in the vesicle size, the leakage of encapsulated Hb and the oxidation of Hb to metHb were not observed. Therefore, the long-term storage of Hb vesicles can be realized as a dry powder.     

Upper and Lower Bounds on Maximum Nonlinearity of n-input m-output Boolean Function

The paper presents lower and upper bounds on the maximumnonlinearity for an n-input m-output Booleanfunction. We show a systematic construction method for a highlynonlinear Boolean function based on binary linear codes whichcontain the first order Reed-Muller code as a subcode. We alsopresent a method to prove the nonexistence of some nonlinearBoolean functions by using nonexistence results on binary linearcodes. Such construction and nonexistence results can be regardedas lower and upper bounds on the maximum nonlinearity. For somen and m, these bounds are tighter than theconventional bounds. The techniques employed here indicate astrong connection between binary linear codes and nonlinear n-input m-output Boolean functions.     

Parametrization of the equations-of-motion method for conjugated hydrocarbons

The equations-of-motion (EOM ) method has been parametrized for the evaluation of the “π → π*” transition energies and moments of conjugated hydrocarbons. In this new semiempirical scheme, the effect of the dynamical screening by σ electrons is explicitly included.     

Search for a simpler synthetic model system for intramolecular 1,3-dipolar cycloaddition to the 5,6-double bond of a pyrimidine nucleoside

In search for a simpler model system for the study of intramolecular thermal reactions between the base and 5'-functionalized sugar moiety in nucleosides, 1-(3-azidopropyl)uracil (2), 1-(4-azidobutyl) pyrimidines (12 and 13) and 1-(5-azidopentyl)-uracil (14) was synthesized through the corresponding ω-benzoyloxy-(6,7 and 8) and ω-hydroxyalkyl-pyrimidines (9,10 and 11). Heating 2 gave 1,N⁶-trimethylene-6-aminouracil (4), while heating 12 and 13 gave N¹-C₆ cleaved addition products. 15 and 16, respectively. 15 was regiospecifically transformed to 1,2,3-triazole derivatives, 17,18 and 19. Heating 1-(4-azidobutyl)-5-bromouracil (20) yielded 3,9-tetramethylene-8-azaxanthine (22). 9 with NBA gave 1,0⁶-tetramethylene-5-bromo-6-hydroxy-5,6-dihydrouracil (24) and the 5-brominated analog of 9 (25). The 4-functionalized butyl side chain proved to serve as a substitute for the 5'-functionalized sugar moiety in pyrimidine ribonucleosides.     

Asymmetric synthesis of dipeptides by means of homogeneous hydrogenation catalyzed by chiral rhodium complexes

Asymmetric hydrogenation of dehydrodipeptides, α-acylaminocinnamoyl-(S)-amino esters, catalyzed by rhodium complexes with chiral diphosphines gave either (R)-N-acylphenylalanyl-(S)-amino esters or (S)-N-acylphenylalanyl-(S)-amino esters with high diastereomeric purity up to 98–99% on using proper chiral ligands.