Artificial glycosyl phosphorylases

alpha- and beta-Cyclodextrin 6(A),6(D)-diacids (1 and 2), beta-cyclodextrin-6-monoacid (14), beta-cyclodextrin 6(A),6(D)-di-O-sulfate (16) and beta-cyclodextrin-6-heptasulfate (19) were synthesised. Acids 1, 2 and 14 were made from perbenzylated alpha- or beta-cyclodextrin, by diisobutylaluminum hydride (DIBAL)-promoted debenzylation, oxidation and deprotection. Addition of molecular sieves was found to improve the debenzylation reaction. Sulfates 16 and 19 were made by sulfation of the appropriately partially protected derivatives and deprotection. Catalysis of 4-nitrophenyl glycoside cleavage by these cyclodextrin derivatives was studied. Compounds 1, 2 and 16 were found to catalyse the reaction, with the catalysis following Michaelis-Menten kinetics and depending first order on the phosphate concentration. In a phosphate buffer (0.5 M, 59 degrees C, pH 8.0), K(M) varied from 2-10 mM and the k(cat)/k(uncat) ratio from 80-1000 depending on the stereochemistry of the substrate and the catalyst, with 2 being the best catalyst and with the sulfated 16 also displaying catalytic ability. The monoacid 14 and the heptasulfate 19 were not catalytic.     

Study of the (p,pn) reaction in light nuclei

The (p, pn) reaction on ²H, ⁶Li, ⁷Li, ⁹Be has been studied at 47 MeV bombarding energy. Excitation energy spectra and energy sharing spectra are presented. Fragmentary information on ¹⁰B, ¹¹B and ¹²C was also obtained. Sequential decay contributions to the ⁶Li(p, pn)⁵Li¹ reaction suggest an admixture of parentage $\text{(α)π(}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)π(}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ for the (3^?), 23 MeV excited state of ⁶Be. A possible 15.5 MeV excited state in ⁶Be is reported. An extensive study of the ⁹Be (p, pn)⁸Be reaction for 45 MeV protons was made. Results for θ_p = θ_n = 25°, 30°, 35°, 40°, 45°, 55°, 65°; θ_n = 40°, θ_p = 25°, 30°, 35°, 40°, 45°, 55°, 65°; θ_p/θ_n = 40°/45°, 38.5° are reported and compared to DWIA calculations. Agreement is good when the lower momentum components of the wave function are sampled, and deteriorates as higher momenta are required. Results are in agreement with the Cohen and Kurath spectroscopic factors for ⁹Be.     

Über rote farbstoffe, die sich vom 2-phenyl-imidazolon-4(5) ableiten

Aqueous solutions of glycyl-benzoyl-imide (I) become dark red on standing for several days or on heating. The red pigments are formed via 2-phenyl-imidazolone-4(5) (II), which can be trapped by reaction with benzaldehyde. Paper electrophoresis using a special buffer system enabled comparison with other red products described in the literature or synthetized otherwise by us. None of them proved to be identical with the “glyoxaline red” of Ruhemann and Stapleton.