Unique Participation of Unprotected Internucleotidic Phosphodiester Residues on Unexpected Cleavage Reaction of the Si?O Bond of the Diisopropylsilandiyl Group Used as a Linker for the Solid‐Phase Synthesis of 5′‐Terminal Guanylated Oligodeoxynucleotides

In connection with the synthesis of guanosine‐capped oligodeoxynucleotides on polymer supports, we found an unprecedented Si O bond cleavage reaction, which occurred when polymer‐linked oligodeoxynucleotides having unprotected internucleotidic phosphate groups were allowed to react with the guanosine 5′‐phosphorimidazolide derivative 18 in the presence of 4‐nitro‐6‐(trifluoromethyl)‐1H‐benzotriazol‐1‐ol (Ntbt‐OH) as an effective activator in pyridine. This side reaction was confirmed by the fact that the liquid‐phase reaction of DMTrTpT O Si(iPr₂)OEt 42 with a simpler model compound, methyl phosphorimidazolide 34 , in the presence of Ntbt‐OH gave DMTrTpT 43 . It turned out that the side reaction hardly occurs without unprotected internucleotidic phosphate groups on oligodeoxynucleotides. The detailed study of this side reaction disclosed that Ntbt‐OH directly attacks the Si‐atom to release oligonucleotides from the resin. It is likely that Ntbt‐OH serves as a very strong nucleophile in pyridine, especially to the Si‐atom of the linker.     

Different generalizations of bags

We consider four different generalizations of bags (alias multisets). We first discuss Yager’s fuzzy bags having different sets of operations. It is shown that one is not a generalization of fuzzy sets but a mapping of them into fuzzy bags, since operations are inconsistent between the two, while the other includes fuzzy sets as particular cases. Third type is called real-valued bags which is simpler than the former two and is a kind of the reduction of fuzzy bags. Finally, the fourth generalization called G-bags includes all three except the first type. It is a minimal extension of the second and the third generalizations. Bag relations are defined for the third type of real-valued bags, which can further be generalized for G-bags.     

An artificial virus-like nano carrier system: enhanced endosomal escape of nanoparticles via synergistic action of pH-sensitive fusogenic peptide derivatives

We previously reported that transferrin (Tf)-modified liposomes (Tf-L) additionally modified with a cholesterylated pH-sensitive fusogenic peptide (Chol-GALA) can release an encapsulated aqueous phase marker to cytosol via endosomal membrane fusion. However, further obstacles need to be overcome to bring the Tf-L to the level of a viral-like gene delivery system. In this study, we developed a novel packaging method to encapsulate condensed plasmid DNA into PEgylated Tf-L (Tf-PEG-L) to form a core–shell-type nanoparticle. The most difficult challenge was to provide a mechanism of escape for the condensed core from endosome to cytosol in the presence of polyethylene glycol (PEG). We hypothesized that a membrane-introduced Chol-GALA and a PEgylated GALA would interact synergistically to induce membrane fusion between liposome and endosome. By simultaneously incorporating Chol-GALA into the membrane of Tf-PEG-L and GALA at tips of PEG chains, a condensed core was released into cytosol, and transfection acitivty increased 100-fold. We concluded that topological control was responsible for the synergistic effect of GALA derivatives introduced on Tf-PEG-L. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Kentaro Sasaki and Kentaro Kogure contributed equally to this work.     

Influence of Amino Acid Composition and Phosphorylation on the Ion Yields of Peptides in MALDI-MS

The influence of arginine (Arg), lysine (Lys), and phenylalanine (Phe) residues and phosphorylation on the molecular ion yields of model peptides have been quantitatively studied using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry in both positive- and negative-ion mode. The results obtained from these experiments have been interpreted from the standpoint of two different components, namely, desorption and ionization, on the basis of the physicochemical properties of constituent amino acids of the model peptides. The presence of basic residues such as Arg and Lys enhanced the ion yields of protonated molecules [M + H]⁺. An N-terminal rather than a C-terminal Arg residue was advantageous for the formation of both [M + H]⁺ and [M – H]^–. The presence of the Phe residue resulted in the increase of the ion yields of both [M + H]⁺ and [M – H]^–. In contrast, the presence of phosphate group(s) contributed to the suppression of the yields of both [M + H]⁺ and [M – H]^– due to the loss of phosphate group. The detection limits for both [M + H]⁺ and [M – H]^– of model peptides have been evaluated.     

A new quassinoid, ailantinol H, from Ailanthus altissima

A new quassinoid, ailantinol H, was isolated from the aerial parts of Ailanthus altissima. The structure was elucidated based on spectral evidence.     

Preconcentration of some phosphorus-containing anions by adsorption on hydrated iron(III) oxide

The adsorption behaviour of orthophosphate, triphosphate, pyrophosphate, monomethylphosphate, phosphite, α- and β-glycerophosphates, dimethylphosphate, and hypophosphite on hydrated iron(III) oxide precipitate is studied as a function of pH. Orthophosphate is adsorbed quantitatively at pH 4.0–8.0, triphosphate and pyrophosphate at pH 4–9.3 and the next three compounds at pH 4–6.8. The last two ions were only slightly adsorbed at any pH examined.