Phosphorylation of 5'-deoxy-5-fluorouridine with inorganic phosphorylating agents

The phosphorylation of 5'-deoxy-5-fluorouridine (doxifluridine, 5'-DFUR) has been achieved using inorganic cyclo-triphosphate (P(3m), Na(3)P(3)O(9)) and monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the reaction of 5'-DFUR with P(3m), 2'-monophospho-5'-DFUR and 3'-monophospho-5'-DFUR were synthesized with a total yield of more than 95%. In the reaction of 5'-DFUR with MCTP, 2'-diphosphoramidophosphono-5'-DFUR and 3'-diphosphoramidophosphono-5'-DFUR were synthesized with a total yield of more than 40%. The phosphorylated products with P(3m) and MCTP were stable in neutral and alkaline solutions.     

Peptide release upon photoconversion of 2-nitrobenzyl compounds into nitroso derivatives

The photoinduced conversion via the aci-nitro into the nitroso form was studied for 4,5-dimethoxy-2-nitrobenzyl alcohols attached to various leaving groups: amino acids histidine (NHis) and aspartate (NAsp) as well as their fluorenylmethoxycarbonyl derivatives (FHis) and (FAsp). In addition, two peptides containing either of the two amino acids were studied, carrying the photoreactive group attached to a histidine (PHis), or to an aspartate (PAsp). The aci-nitro forms with maximum at λ(aci) = 420 nm were observed for FHis and FAsp after the decay of a triplet-triplet absorption, analogous to those of other 2-nitrobenzyl type compounds. For both FHis and FAsp the quantum yield of photoconversion Φ(p) is 0.03 and for the peptides PHis and PAsp ca 0.01 and 0.005, respectively.     

Structure and dynamics of water in mixed solutions including laponite and PEO

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.     

Synthetic utilization of 2-chloro-1,1,1,2-tetrafluoroethane

β-Substituted α-fluoro-α,β-unsaturated carboxylic acids have been successfully synthesized, usually in a (Z)-stereospecific manner by way of a stepwise or a one-pot three-step procedure starting from 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), one of the major byproducts of the industrial process for tetrafluoroethene formation from chlorofluoromethane (HCFC-22).     

Identification of 3-enol sulfate of Cypridina luciferin,Cypridina luciferyl sulfate,in the sea-firefly Cypridina (Vargula) hilgendorfii

Cypridina luciferin from the luminous ostracod Cypridina (Vargula) hilgendorfii has an imidazopyrazinone core structure (3,7-dihydroimidazopyrazin-3-one), which is identical to that of coelenterazine. Cypridina luciferyl sulfate (3-enol sulfate of Cypridina luciferin) was isolated for the first time and the chemical structure was identified by LC/ESI–TOF–MS analysis. Furthermore, Cypridina luciferyl sulfate was chemically synthesized, and its absorption and MS/MS spectra were in agreement with that of Cypridina luciferyl sulfate isolated. Using the crude extracts of Cypridina specimens, Cypridina luciferyl sulfate could be converted to Cypridina luciferin in the presence of adenosine 3′,5′-diphosphate (PAP), and Cypridina luciferin was converted to Cypridina luciferyl sulfate in the presence of 3′-phosphoadenosine 5′-phosphosulfate (PAPS). These results suggested that a sulfotransferase catalyzes the reversible sulfation of Cypridina luciferin in Cypridina hilgendorfii. In aqueous solution, Cypridina luciferyl sulfate was more stable than Cypridina luciferin and might be a storage form of Cypridina luciferin.     

Facile synthetic protocols for perfluoroalkyl-substituted diazapentaphenes

Novel syntheses of 13,14-bis(perfluoroalkyl)-substituted 5,8-diazapentaphene derivatives were realized by such a facile two-step protocol as consecutive benzyne insertion into C(O)–NH bonds of p-phenylene-bis(perfluoroalkanamides), followed by Friedel–Crafts type cyclization reaction, yielding the corresponding title compounds especially for the case of Rf=CF₃ or C₂F₅. Additionally, an alternative approach based on condensation of cyclohexane-1,4-dione with (o-aminophenyl) perfluoroalkyl ketones, followed by dehydrogenation enabled us to effectively access to the same final products in better yields.     

On the holomorphic torus-Bott tower of aspherical manifolds

We introduce a notion of holomorphic torus-Bott tower which is an iterated holomorphic Seifert fiber space with fiber a complex torus. This is thought of as a holomorphic version of a real Bott tower. The top space of the holomorphic torus-Bott tower is called a holomorphic torus-Bott manifold. We discuss the structure of holomorphic torus-Bott manifolds and particularly the holomorphic rigidity of holomorphic torus-Bott manifolds.     

Thermogravimetric analysis with gas chromatograph mass spectrometry of Japanese fir wood (Abies sachalinensis) in helium with or without steam–oxygen

Thermal properties of a kind of Japanese fir wood (Abies sachalinensis) were thermogravimetrically analyzed and produced compounds were gas chromatograph mass spectrometrically analyzed for basic study of biomass gasification. Atmosphere during each analysis was controlled to be helium alone or helium with steam–oxygen. Compounds identified in this series of measurements were roughly classified into three groups: (a) phenol and its derivatives, (b) oxygenated cyclic compounds, and (c) oxygenated compounds of low molecule. Their production rates were dependent on both temperature and atmosphere, which well explained high carbon conversion rate from feedstock to gas of advanced gasification technologies, such as entrained-flow type gasification, and high yields of solid and liquid residues of traditional gasification technologies, such as fixed-bed type gasification.     

Base-Catalyzed Polymerization of Vinyl Acetamide and Allyl Cyanide

The base-catalyzed polymerizations of vinyl acetamide and allyl cyanide have been studied. It was found by chemical and spectroscopic analyses that the polymer obtained from vinyl acetamide was poly(2-methyl-β-alanine), which was the same structure as the polymer prepared by base-catalyzed polymerization of crotonamide. It is concluded, therefore, that vinyl acetamide was polymerized through the isomerization of allyl group and the proton transfer reaction from amide group. The gas-chromatographic analysis of the polymerization system showed that vinyl acetamide was consumed faster than crotonamide. This, fact suggests that an intermediate other than crotonamide might be present in the process of isomerization of vinyl acetamide. On the other hand, in the base-catalyzed polymerization of allyl cyanide, the allyl group was isomerized, but the reaction of cyanide group hardly occurred.