Some triplet energy-transfer reactions initiated by photoexcitation of triplet excited state of dibenz[a,h]anthracene to the higher triplet excited states

Some triplet energy-transfer reactions initiated by photoexcitation of the triplet excited state of dibenz[a,h]anthracene to higher triplet excited states (DBA(T_n)) were observed in the presence of the triplet energy quenchers (Q) such as naphthalene, biphenyl, p-dichlorobenzene, and o-dicyanobenzene. In the case of carbon tetrachloride (CCl₄) as Q, DBA(T_n)-sensitized decomposition of CCl₄ occurred.     

Novel phenoxyalkylamine derivatives. VII. Synthesis and pharmacological activities of 2-alkoxy-5-[(phenoxyalkylamino)alkyl]benzenesulfonamide derivatives.

To find a novel alpha-blocker with high alpha-blocking selectivity against dopamine D2-receptor affinity, we performed structural modification of the alkylene chains and the substituents on two benzene rings of 2-alkoxy-5-[(phenoxyalkylamino)alkyl]benzenesulfonamide derivatives. The modification of the alkylene chain between the amino moiety in the center of the molecule and the benzene ring (ring A) was found to be the most significant. 5-[2-[[2-(5-Fluoro-2-methoxyphenoxy)ethyl]amino]propyl]-2- methoxybenzenesulfonamide (II-4), which possesses 1-methylethyl as the alkylene chain, exhibited high alpha-blocking selectivity as well as potent alpha-blocking activity.     

Ruthenium-catalyzed carbonylative cycloaddition of alpha-keto lactones with alkenes or alkynes: the participation of an ester-carbonyl group in cycloaddition reactions as the two-atom assembling unit

The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction.     

Synthesis and antinociceptive activity of orally active opioid peptides: improvement of oral bioavailability by esterification

To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l).     

Remarkable reactivities of the xanthone ketyl radical in the excited state compared with that in the ground state

The properties and reactivities of the xanthone (Xn) ketyl radical (XnH*) in the doublet excited state (XnH*(D1)) were examined by using two-color two-laser flash photolysis. The absorption and fluorescence of XnH*(D1) were observed for the first time. Several factors governing the deactivation processes of XnH*(D1) such as interaction and reaction with solvent molecules were discussed. The remarkable change of reactivity of XnH*(D1) compared with that in the ground state (XnH*(D0)) was indicated from the experimental results. The rapid halogen abstraction of XnH*(D1) from some halogen donors such as carbon tetrachloride (CCl4) was found to occur. The halogen abstraction occurred more efficiently in the polar solvents than in the nonpolar solvents. It is suggested that the polar solvents promote the spin distribution of XnH*(D1) of the phenyl ring favorable to the halogen abstraction.     

Nitriding of titanium with plasma jet under reduced pressure

The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10^–10–10^–8 g² cm^–4 s^–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed.     

Development of novel chiral urea catalysts for the hetero-Michael reaction

Chiral urea compounds 10a-g were synthesized as catalysts for conjugate addition of pyrrolidine (2) to gamma-crotonolactone (3). In the presence of a catalytic amount of the chiral ureas, this hetero-Michael reaction was greatly accelerated. Asymmetric induction was observed with the catalysts 10e, 10f, and 10g.     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997     

Preparation of Silica-Silk Fibroin-Polyurethane Composite Films via a Sol-Gel Route

A tetraethoxysilane (TEOS)-derived sol aged for 0 h–6 h at room temperature was mixed with a polyurethane (PU) matrix. A composite of silk fibroin (SF) powders and acrylamide (AAm) was dispersed in the sol-PU mixture and dried isothermally at temperatures between 25°C and 120°C to obtain composite films. Three competitive reactions take place, i.e., those between silica-silica, SF-PU and silica-organic phases, during formation of the composite films. These reactions determine the properties such as morphology and homogeneity of the composite films. IR absorption bands for amide groups (–CONH–), C=O (amide I, 1730 cm^–1) and N–H (amide II, 1530 cm^–1) become larger with decreasing aging time of TEOS-derived sol, or increasing drying temperature. DTA exothermic peak due to the thermal decomposition of SF-AAm composite, on the composite films prepared from the 0 h-aged sol or dried at more than 50°C, shifts toward higher temperature by 44 K or more than 63 K respectively, as compared to the SF-AAm composite. Shorter aging time of TEOS-derived sol and higher drying temperature increased the extent of dispersibility, among SF-AAm composite, PU and silica, to bring a composite film more homogeneous.     

Cross-linking chemistry and biology: development of multifunctional photoaffinity probes

An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions.