SPECTROSCOPY AND FLUORESCENCE QUENCHING OF TYROSINE IN LIMA BEAN TRYPSIN/CHYMOTRYPSIN INHIBITOR AND MODEL PEPTIDES

The effects of citrate ion concentration and pH on the optical spectra and fluorescence decay have been measured for several tyrosine model compounds and lima bean trypsin/chymotrypsin inhibitor, a protein containing one tyrosine at position 69 and seven disulfides but no tryptophan, in order to determine the location and environment of Tyr 69. Tyrosine in the protein is protected from citrate collisional quenching, as indicated by the dynamic quenching constant 9 to 15 times smaller than those for the model peptides. Static quenching remains, with a Stern-Volmer constant of about 1.0 M-1, somewhat smaller than those of L-tyrosine, tyrosine-glutamate, and leucine-tyrosine-leucine. The elevated pKa of Tyr 69, greater than or equal to 11.6, also indicates protein protection from solvent ions. Though Coulomb repulsion of the Glu 70/citrate pair may play a role in the shielding of Tyr 69 from citrate, our measurements indicate that steric effects of the protein structure are more important. Tyrosinate emission in the protein at neutral pH is minimal.     

Regioselective synthesis and properties of novel [60]fullerene bisadducts containing a dibenzocrown ether moiety

The reactions of [60]fullerene with bis-o-quinodimethane precursors 3, 4, and 5 containing a dibenzo-18-crown-6, 24-crown-8 and 30-crown-10 moiety, respectively, were investigated. Both 3 and 4 provided trans-4 bisadducts 6a and 7a, respectively, as major product, though the selectivity in the latter was lower than that in the former. As minor product, 6b (cis-2) was produced from 3, while 7c (e) as well as 7b (cis-2) were produced from 4. Precursor 5 exclusively afforded e bisadduct 8 without any other regioisomers. These bisadducts showed different ionophoric properties from one another; for instance, 6a and 7b exhibited a high complexing ability toward the K+ ion, while 6b hardly showed complexation with any alkali metal ions. The selectivity coefficients (K(Na,K)(pot)) of 6a and 7b toward K+ over Na+ ion, determined with an ion-selective electrode, were much higher than that of dibenzo-18-crown-6.     

Diacetylene-containing polymers,II. Polyesters and polyurethanes containing m,m′-butadiynylenedibenzyl groups

Diacetylene-containing polyesters and polyurethanes were prepared by the reaction of m,m-butadiynylenedibenzyl alcohol with isophthaloyl chloride, sebacoyl chloride, hexamethylene diisocyanate and 2,4-tolylene diisocyanate. Their thermal behavior was studied by optical microscope and differential scanning calorimetry (DSC). The polyesters were crystalline. The polyurethane prepared from hexamethylene diisocyanate and polyphthalates crystallized on cooling from their melts. All turned a reddish brown color on heating at temperatures above 200°C, and prolonged heating led to a black resin, but thermal decomposition could not be avoided. Irradiation by γ-ray and UV light at room temperature deepened the color of the films, but the polymerization of the diacetylene groups was not appreciable. Simultaneous heating and irradiation was necessary to obtain transparent, amorphous, wine red colored films.     

Effects of trivalent phosphorus compounds on vinyl polymerizations—VII. A nonstationary state radical polymerization of methylmethacrylate in the presence of phenyldichlorophosphine

In the radical polymerization of methylmethacrylate in the presence of p-phenyldichlorophosphine, the initial rate and degree of polymerization increased with polymerization time. They first decreased with increase in the phosphine concentration but increased with further increase in the phosphine concentration. Termination was first order with respect to the initiator. The degree of polymerization was independent of the initiator concentration, but dependent on the conversion. The polymer contained no phosphorus units regardless of the phosphine concentration. The ESR spectra of system showed existence of a phosphorus radical. In order to explain these characteristics of the polymerization, it is proposed that there may be a nonstationary state in which the polymer radicals are regenerated during the polymerization from the phosphoranyl radicals.     

Room Temperature Solid State Reaction Involving Structural Transformation of Covalent Oxide Network

An interesting structural transformation from a two dimensional (2d) covalent oxide network with a layered structure to a three-dimensional (3d) network with a tunnel structure was found at room temperature in the mixture of hydrated alkali-metal molybdenum bronze and amorphous alkali-metal molybdate. From various experimental results it was concluded that the transformation was due to a room temperature solid state reaction.     

Facile S-alkyl thiocarbamate synthesis by a novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur

A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of S-alkyl thiocarbamate is observed. The present DBU-assisted carbonylation can also be applied to new synthetic methods for benthiocarb and orthobencarb (herbicides) and carbamoyl chlorides.     

Fluorination of 2-alkyl-substituted oxanes. The synthesis and purification of perfluoro(2-alkyl-substituted oxane)s

Five kinds of 2-alkyl-substituted oxanes like 2-ethyloxane, 2-n-propyloxane, 2-iso-propyloxane, 2-n-butyloxane and 2-n-amyloxane were fluorinated electrochemically to give the corresponding perfluoro(2-alkyloxane)s. The perfluoro(2-alkyloxane)s were obtained in good yields from these starting materials together with isomeric perfluoro(2-alkyloxolane)s, perfluoro(2-alkyl-5-methyloxolane)s and perfluoro(dialkyl ether)s. The purification of the perfluoro(2-alkyloxane)s which contained small amounts of isomeric perfluoro(2-alkyloxolane)s was successfully achieved by recovering the former unreacted after treating these mixture with anhydrous aluminum chloride at 150 /sR 160 °C during /sR 48 hrs in order to convert the latter into the easy-separable perfluoro(2,5,5- trichloro-2-alkyloxolane)s. Small quantities of new perfluoro(5,5-dichloroalkanoyl chloride)s were also among the chlorination products. The spectroscopic data as well as the physical properties of these new fluorination products, and perfluoro(2,5,5-trichloro-2-alkyloxolane)s and perfluoro(5,5-dichloroalkanoyl chloride)s are presented.     

Three new quassinoids,ailantinol E,F, and G,from Ailanthus altissima

Three new quassinoids, ailantinol E (1), ailantinol F (2), and ailantinol G (3), and related compounds were isolated from Ailanthus altissima grown in Taiwan. Their structures were elucidated from spectral evidence. Each new quassinoid was evaluated for its antitumor promoting effects against Epstein-Barr virus early antigen activation introduced by 12-O-tetradecanoylphorbol-13-acetate in Raji cells. The new quassinoids were found to show potent activity without showing any cytotoxicity. The screening for inhibitors against nitric oxide donor action was also conducted using the new quassinoids and some standard samples.