| Project/Area Number |
16310144
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Living organism molecular science
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| Research Institution | Hokkaido University |
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Principal Investigator |
MONDE Kenji Hokkaido University, Faculty of Advanced Life Science, Dr. Associate Professor (40210207)
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| Co-Investigator(Kenkyū-buntansha) |
MIURA Nobuaki okkaido University, Faculty of Advanced Life Science, Dr. Research Associate Professor (80372267)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,620,000 (Direct Cost: ¥15,600,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2007: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2006: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2005: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2004: ¥5,400,000 (Direct Cost: ¥5,400,000)
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| Keywords | VCD / vibrational circular dichroism / glycoside bond / stereochemistry / enzymatic reaction monitoring / conformational analysis / absolute configuration / DFT calculation / α-グリコシドバンド / 脂質 / 芳香族グリコシド / 立体化学 / シアル酸 / 糖脂質 / グリセロ脂質 / 含臭素海洋天然物 / ファイトアレキシン / メチルグリコシドバンド / 酵素モニタリング / オリゴ糖 / 加水分解酵素 |
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| Research Abstract |
Structural studies of carbohydrates have required development of analytical tools. VCD spectroscopy has been of potential use, but its application to carbohydrates has been limited compared to proteins and nucleic acids partly due to the difficulties in the interpretation of the spectra. Through the systematical carbohydrate measurements, we have found an intense VCD peak appeared around 1145 cm^<-1> characteristic for axial glycosidic sugars i.e. the glycoside band. Isotope substitution indicated the profound participation of the anomeric moiety in the vibration of this band. To predict its vibrational mode by means of density functional theory (DFT) calculation, properly designed model compounds were prepared and their calculated spectra were compared with the observed ones. In this study, for the first time, carbohydrate VCD spectra were reliably predicted. Furthermore, the sign of the glycoside band was found to reflect not only the anomeric configuration but also the pyranose conf
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ormation. The isotropic and theoretical studies characterized its vibrational mode as the C1-H1 deformation coupled with C1-O1 stretching, which indicated the applicability to more complicated glycoconjugates. Finally, VCD technique was first applied to glycopeptides, and demonstrated the simultaneous analysis on both the carbohydrate and aglycan parts.
Systematic VCD studies of N-acetylneuraminic acid (Neu5Ac), a recognition related unique carbohydrate, were performed for the first time. Two pairs of anomeric isomers regarding a quaternary C2 asymmetric carbon of Neu5Ac derivatives were synthesized. VCD spectral patterns around the ester carbonyl region, as well as other Mid-IR regions would be practical markers to distinguish the C2 stereochemistry.
Other applications of the VCD technique were also applied to biologically active compounds such as chiral cruciferous phytoalexins and the antidote like compound against snake venom ((+)-alternamin), leading to successful assignments of their stereochemistries in solution station with the aids of their DFT theoretical calculations. Less
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