Prolonged production of hydrogen gas by a chloroplast biocatalytic system.

The evolution of H₂ gas in an $\text{in vitro}$ illuminated chloroplast plus hydrogenase system was shown to function for six and a half hours at a continuous rate of about 10 μmoles H₂/mg. chlorophyll/hour. Chloroplasts from various plant species, using different isolation media, and storage in a fixed state (glutaraldehyde) at 4°, ?5° and ?196° were shown to catalyze H₂ production. Both $\text{Clostridium}$ and $\text{E. coli}$ hydrogenase were used. From the use of the photosystem II inhibitors DCMU and DBMIB and heat inactivation of photosystem II, it was concluded that H₂O was the source of electrons for H₂ gas production.     

Structure and anomeric configuration of the C-nucleoside analogs obtained by dehydration of 7-deoxy-l-manno-2-heptulose phenylosazone

Dehydration of 7-deoxy-l-manno-2-heptulose phenylosazone with methanolic sulfuric acid afforded two 3,6-anhydro-osazone derivatives (2 and 3). Refluxing the anhydro-osazones with copper sulfate gave two C-nucleoside analogs, namely, 4-(5-deoxy-α-l-arabinofuranosyl)-2-phenyl-ν-triazole (4) and 4-(5-deoxy-β-l-arabinofuranosyl)-2-phenyl-ν-triazole (5). The structure and anomeric configurations of 2, 4, and 5 were determined by n.m.r. spectroscopy. The preponderant conformation of 4 and 5, and the mass spectra of 2, 4, and 5 are discussed.     

The behavior of some aldoses with 2,2-dimethoxypropane-N,N-dimethylformamide-p-toluenesulfonic acid. II. At 80 degrees

Four aldohexoses were individually subjected to the reagent mixture and temperature cited in the title; in each case, the 2,2-dimethoxypropane was present in only a small molar excess and the p-toluenesulfonic acid was used in trace amounts. D-Mannose (1) afforded the known 2,3:5,6-di-O-isopropylidene-D-mannofuranose (2) in significantly higher yield than when the reaction was conducted at room temperature. The other three aldoses, however, gave products markedly different from those formed under the milder conditions. 2-Acetamido-2-deoxy-D-mannose (3) gave a mixture of products from which methyl 2-acetamido-2-deoxy-2,3-N,O-isopropylidene-5,6-O-isopropylidene-α-D-mannofuranoside (4), 2-acetamido-2-deoxy-2,3-N,O-isopropylidene-5,6-O-isopropylidene-D-mannofuranose (5a), and methyl 2-acetamido-2-deoxy-5,6-O-isopropylidene-α-D-mannofuranoside (6a) were isolated. 2-Acetamido-2-deoxy-D-galactose (11) gave compounds identified as methyl 2-acetamido-2-deoxy-5,6-O-isopropylidene-β-D-galactofuranoside (12a) and methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-β-D-galactopyranoside (13a). 2-Acetamido-2-deoxy-D-glucose (16) afforded methyl 2-acetamido-2-deoxy-5,6-O-isopropylidene-β-D-glucofuranoside (17a) and methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-β-D-glucopyranoside (18a). Evidence in support of the structures assigned to these new derivatives is presented.     

The application of 13C-n.m.r. spectroscopy to products derived from sucrose

Glycogen has been isolated from the livers of rats which had been fasted and then intubated with d-glucose. The structure of the glycogen, as determined by iodine staining and enzymic methods, was shown to be very similar to that from control animals. There were slight differences in the iodine-staining properties, but not as marked as that previously reported in the literature.     

The synthesis and N.M.R. spectroscopy of derivatives of 6-amino-6-deoxy-D-galactose-6-15N

Derivatives of 6-amino-6-deoxy-D-galactose-6-¹⁵N have been synthesized by reaction of the 6-deoxy-6-iodo (1) or 6-O-p-tolylsulfonyl derivative of 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose with potassium phthalimide-¹⁵N. The reaction of 1 also yielded an elimination product, 6-deoxy-1,2:3,4-di-O-isopropylidene-β-L-arabino-hex-5-enopyranose. The structures of the 6-amino-6-deoxy-D-galactose derivatives and their precursors were characterized by proton- and ¹³C-n.m.r. spectroscopy, with confirmation of the ¹³C assignments by selective proton decoupling. Selective broadening of the C-1, C-4, C-5, and C-6 resonances of 6-amino-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose by low concentrations of cupric ion was observed, and studied by computerized measurements of the ¹³C linewidths. The application of this broadening to ¹³C-spectral assignments of amino sugar derivatives is indicated.     

Synthesis of the repeating unit of the teichoic acid isolated from the cell wall of bacillus subtilis VAR. niger WM

Stereocontrolled synthesis of 1-O-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-2,3-O-isopropylidene-D-glycerol (6) was achieved in good yield by use of the modified, orthoester method. Compound 6 was then transformed into 1-deoxy-3-O-phosphono-D-glycerol-1-yl β-D-glucopyranoside (1), identical with the repeating unit of the teichoic acid isolated from the cell wall of Bacillus subtilis var. niger WM, in a regio-controlled way, unambiguous evidence for the assignment of the stereochemistry of the natural product being provided by the ¹³C-n.m.r. data for 1 and its L-glycerol-1-yl isomer.     

A new method for the determination of N-sulfate in heparin and its analogs.

A new method for the determination of N-sulfate in heparin and its analogs is described. The method is based on the determination of inorganic sulfate liberated by deamination with nitrous acid. The accuracy, simplicity, and validity of this method are evaluated by comparing it with previous methods.     

Isolation and characterisation of lignin-carbohydrate complexes from the milled-wood lignin fraction of Pinus densiflora sieb. et zucc.

The lignin-carbohydrate complex (LCC-W), isolated from the milled-wood, lignin fraction of Pinus densiflora Sieb. et Zucc., comprised three fractions (W-1,2,3) by gel filtration on Sepharose 4B. W-1 was eluted at the void volume, whereas W-2 and W-3 were included in the gel and had apparent weight-average molecular weights of 5.0 × 10⁵ and 5.0 × 10³, respectively. W-2 and W-3 were homogeneous in ultracentrifugal and electrophoretic analyses. The sedimentation coefficients of W-2 and W-3 were 25.7 and 0.4S, respectively. The chemical composition of W-2 was 38.0% of neutral sugar, 6.2% of uronic acid, 51.5% of lignin, and the corresponding values for W-3 were 73.1, 11.0, and 22.2%. The neutral carbohydrate residues of W-2 and W-3 were l-arabinose, d-xylose, d-mannose, d-galactose, and d-glucose in the ratios 15.8:16.2:37.3:16.7:14.0 and 27.6:16.5:26.1:19.3:10.5, respectively. Based on the results of methylation and Smith-degradation analyses, the carbohydrate moiety of the LCC-W fractions was found to be multiply branched. The major backbone structure was composed of (1→4)-linked d-mannopyranosyl residues. By hydrophobicinteraction chromatography on Phenyl- and Octyl-Sepharsoe CL-4B gels, it is concluded that the LCC-W fractions have a hydrophobic property that is exclusively ascribed to the lignin moiety.     

Synthesis of a C-nucleoside analog of the antibiotic cordycepin

A C-nucleoside analog of cordycepin, 6-amino-8-(3-deoxy-β-D-erythro-pentofuranosyl)purine (6), has been synthesized. 3-Deoxy-2,5-di-O-(p-nitrobenzoyl)- β-D-erythro-pentofuranosyl bromide reacted with mercuric cyanide in nitromethane to give 2,5-anhydro-4-deoxy-3,6-di-O-(p-nitrobenzoyl)-D-ribo-hexononitrile which, after acid hydrolysis and removal of the protecting groups, afforded 2,5-anhydro-4-deoxy-D-ribo-hexonic acid. Reaction of this acid with 4,5,6-triaminopyrimidine gave the corresponding amide, which was pyrolyzed to give compound 6. The mass- and n.m.r.-spectral data for the synthesized analog are quite similar to those of the natural antibiotic.     

Insulin-like,and insulin-antagonistic,carbohydrate derivatives. The synthesis of aryl and aralkyl d-mannopyranosides and 1-thio-d-mannopyranosides

A number of novel, aryl and aralkyl d-mannopyranosides and 1-thio-d-mannopyranosides were synthesized for evaluation of insulin-like and insulin-antagonistic properties. The substituted-phenyl α-d-mannopyranosides were prepared by the general procedure of Helferich and Schmitz-Hillebrecht, the substituted-phenyl 1-thio-α-d-mannopyranosides by a method corresponding to the Michael synthesis of aromatic glycosides, and the aralkyl 1-thio-α-d-mannopyranosides by aralkylation of 2,3,4,6-tetra-O-acetyl-1-thio-α-d-mannopyranose (15) and subsequent O-deacetylation. Compound 15 was obtained by basic cleavage of the amidino group in 2-S-(tetra-O-acetyl-α-d-mannopyranosyl)-2-thiopseudourea hydrobromide, the product of the reaction of tetra-O-acetyl-α-d-mannosyl bromide with thiourea. Benzyl 1-thio-β-d-mannopyranoside, obtained by reaction of the sodium salt of 1-thio-β-d-mannopyranose with α-bromotoluene, and benzyl 1-thio-α-l-mannopyranoside were also synthesized, in order to assess the stereospecificity of the biological activities measured.