Preparation and evaluation of unimolecular pentavalent and hexavalent antigenic constructs targeting prostate and breast cancer: a synthetic route to anticancer vaccine candidates

Several novel, fully synthetic, carbohydrate-based antitumor vaccines have been assembled. Each construct consists of multiple cancer-related antigens displayed on a single polypeptide backbone. Recent advances in synthetic methodology have allowed for the incorporation of a complex oligosaccharide terminating in a sialic acid residue (i.e., GM2) as one of the carbohydrate antigens. Details of the vaccine synthesis as well as the results of preliminary immunological investigations are described herein.     

Photoacoust1C Studies on Very Thin Poly(Methyl Methacrylate) Films Prepared by a Cast1Ng-On-Water Method

Photoacoustic (PA) responses from very-thin poly(methyl methacrylate) (PMMA) films were investigated at various lamination conditions. The PA signal increased when the dye-doped films were laminated up to five layers, but tended to saturate beyond five layers. When the blank films were superimposed on the dye-doped film, the signal became smaller. The signal was larger when the dye-doped film was arranged outermost in the laminated film assembly of dye-doped and blank films. The results imply the effect of film vibration on the PA response.     

A strategy for the development of small-molecule-based sensors that strongly fluoresce when bound to a specific RNA

We report a broadly applicable approach for the development of small-molecule-based RNA sensors. Our photoinduced electron transfer (PET) sensor consists of a fluorescein derivative as the fluorophore and two aniline derivatives as electron donors (quenchers). The isolation of electron-donor-binding RNA by in vitro selection (also known as SELEX) yielded an RNA aptamer that could increase the fluorescence intensity of the sensor by 13-fold. This result shows that RNA-electron-donor interactions can be used to develop modular RNA chemosensors.     

Stereocontrolled syntheses of alpha-C-mannosyltryptophan and its analogues

The total synthesis of alpha-C-mannosyltryptophan (C-Man-Trp), a naturally occurring C-glycosylamino acid, was achieved from a commercially available alpha-methyl-D-mannoside in 10 steps including the following key steps: the C-glycosidation of a mannose derivative with a stannylacetylene, Castro indole synthesis, and Sc(ClO4)3-promoted coupling with L-serine-derived aziridine carboxylate. The glucose- and galactose-analogues of C-Man-Trp were also synthesized in a similar manner. Conformational analyses of the synthesized C-glycosyltryptophan and its synthetic intermediate are briefly discussed.     

Steric interaction of solvation and sterically enhanced halogeno complexation of manganese(II), cobalt(II) and nickel(II) ions inN,N-dimethylacetamide

The complexation of manganese(II), cobalt(II) and nikel(II) with bromide ions has been studied in N,N-dimethylacetamide(DMA) by calorimetry and spectrophotometry. The formation of [MBr]⁺, [MBr₂] and [MBr₃]^– (M=Mn, Co, Ni) was revealed in all the metal systems. Interestingly, the complexation is significantly enhanced in DMA over N,N-dimethylformamide (DMF). This is unusual because physicochemical properties of DMA and DMF as solvent are similar. Furthermore, extracted electronic spectra of individual complexes of Ni^II suggested the presence of a geometry equilibrium, [NiBr(DMA)₅]⁺=[NiBr(DMA)₄]⁺+ DMA, in DMA. A similar geometry equilibrium is also suggested, [NiBr₂(DMA)₃]=[NiBr₂(DMA)₂]+DMA. Such geometry equilibria were not observed in DMF. With regard to cobalt(II), electronic spectra show the presence of the four-coordinated [CoBr(DMA)₃]⁺ complex in DMA, unlike the six-coordinated [CoBr(DMF)₅]⁺ one in DMF. These facts suggest that a specific strong steric interaction operates between coordinating solvent molecules, which plays a key role in the complexation behavior of the divalent transition metal ions in DMA.