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1 Division of Biofunctional Chemistry The Chemical Society of Japan Vol. 19, No.3 ( )

2

3 Chem. & Eng News (Oct. 25, 2004) Insight Nobel Prizes and Fuzzy Boundaries Experience shows you don t have to be a chemist to win the Nobel Prize in Chemistry Wennerstr Lund Univ Perutz Kendrew Watson, Crick Wilkins - 2 -

4 Top Scientist 63 ERATO ICORP SORST COE 21COE Izatt-Christensen 1998 Backer Lecture 1999 Vielberth Lectureship ISI-Thomson Scientific

5 ON-OFF ON-OFF 1), 3) 1. N N Zn N N N N N Zn Zn N N N Zn N N (NO 3 ) 4 (NO 3 ) , Fluorescence titration curve of 1 with the phosphorylated Fluorescence Intensity (a.u.) F/Fo-1 0 Wavelength (nm) peptide (µm) Fluorescence Spectrum change of 1 (1 µm) upon the addition of a phosphorylated peptide (EEEIpYEEFD) (Inset) peptide (l ) and the corresponding non-phosphorylated peptide (s ).

6 M -1 (Figure 1) 10 3 M -1 Dpa-Zn(II) 1 X 2 1, 2 PET Zn P Zn 2. 1, 2 3, 4 2) N Zn N N N N N N Zn Zn N N N N 3 N N 4 N N Zn N - 5 -

7 CD 3, 4 3 i, i+7 (K app = 1.6 x 10 6 M -1 ) α- α- 3, ) i) ii) 1, 2 PTP1B PTP1B 4) SDS-PAGE (SDS-PAGE) 2 iii) WW 4-6 -

8 WW 1) Akio Ojida, Yasuko Mito-oka, Masa-aki Inoue, Itaru Hamachi J. Am. Chem. Soc. 2002, 124, ) Akio Ojida, Masa-aki Inoue, Yasuko Mito-oka, Itaru Hamachi J. Am. Chem. Soc. 2003, 125, ) Akio Ojida, Yasuko Mito-oka, Kazuki Sada, Itaru Hamachi J. Am. Chem. Soc. 2004, 126, ) Akio Ojida, Takahiro Kohira, Itaru Hamachi Chem. Lett. 2004, 33,

9 S 400 nm 2λ (800 nm λ 800 nm 400 nm (400 nm) 2λ (800 nm (PDT) PDT PDT PDT S 0 1. p 1) 2) (3) ( ) ( ) (4D) 3) (5D) - 8 -

10 2. 6 (7P) GPC (8) 8 (5D) GPC 3. 5D :4D :W avelength /nm s (2) Z-scan D 4D s (2) nm 370 GM D s (2) nm 7600 GM 4D σ ( 2) / G M

11 (5M) (7M) (8) 5M 7M 5D 7P M s (2) 5D 1/ GM 5M 1800 GM 7M 1200 GM GM 2 5) sample 4D 5D 5M 7M 8 σ (2) / GM GM GM PDT GM 5D 7600 GM 4000 PDT 4. PDT QOL 630 nm PDT 5D PDT 733 nm 1270 nm 5D PDT (9)

12 5D HeLa PDT PDT PDT PDT 1) (a) Albota, M. et al. Science 1998, 281, 1653; (b) Reinhardt, B. A. et al. Chem. Mater. 1998, 10, ) (a) Ogawa, K.; Kobuke, Y. Angew. Chem., Int. Ed. 2000, 39, 4070; (b) Kobuke, Y.; Ogawa, K. Bull. Chem. Soc. Jpn. 2003, 78, ) Ogawa, K.; Zhang, T.; Yoshihara, K.; Kobuke, Y. J. Am. Chem. Soc. 2002, 124, 22. 4) Ogawa, K.; Ohashi, A.; Kobuke, Y.; Kamada, K.; Ohta, K. J. Am. Chem. Soc. 2003, 125, ) Zhou, X; Ren, A.-M.; Feng, J.-K. Chem. Eur. J. 2004, 10,

13 - DNA (1) DNA(ssDNA) (2) ssdna - (POC) (3) (APEG) - 1 (A) 5 - ssdna (B) DNA POC (C) APEG DNA DNA (D) (POC) (A) DNA(ssDNA) (B) POC (C) APEG (D)

14 1. POC A(RNase A) 2 RNase A 20 S-peptide 104 (S-protein) i RNase S-peptide POC S- peptide-s-protein POC APEG 2 POC ii 19 mer S-peptide FastMoc iii N HS-(CH 2 ) 6 -CGA CGT TGT AAA ACG ACG GCC AGT-3 HPLC HPLC MALDI TOF-MS APEG PEG(M r =4000) mm NaCl DNA 3.3 x 10 4 M -1 iv n=9 2. (A) - (POC) (B) APEG. POC (QCM) v 3 QCM (2.5 mmφ, 4.9 mm 2 ) - 5 -SH ssdna(poc ) ssdna POC ( 3A ) QCM (Affinix Q vi,

15 Initium, Inc.) APEG ( 3A ) APEG POC 3B DNA QCM 3. QCM APEG (A) ssdna POC ( ) APEG ( ) APEG (B) DNA ( ) APEG ( ) ssdna APEG ( ) 2. POC - PEG S-peptide S-peptide PEG S-protein S-peptide-S-protein QCM 2 (BSA)(pI=4.7) A(RNase A)(pI=9.3) APEG BSA POC A B 4. - APEG (A) APEG BSA ( ) S-protein ( ) (B) APEG BSA ( ) S-protein ( )

16 QCM ( 4A) BSA S-protein BSA S- peptide-s-protein POC QCM APEG BSA S-protein ( 4B) APEG POC BSA RNase A 4B (data not shown) APEG DNA vii i) R. T. Raines, Chem. Rev., 98, (1998). ii) N. J. Ede, G. W. Tregear and J. Haralambidis, Bioconjugate Chem., 5, 373 (1994). iii) K. Ohtsuka, R. Kajiki, M. Waki, T. Nojima and S. Takenaka, Analyst, 129, (2004). iv) K. Ohtsuka, K. Uemura, T. Nojima, M. Waki and S. Takenaka, in preparation. v) S. Fukusho, H. Furusawa and Y. Okahata, Chem. Commun., 2002, (2002). vi) vii)

17 1 1. RNA N RNA N RNA RNA 1A, B N RNA N RNA 1C RNA

18 N RNA RNA 1B RNA RNA (A) N RNA (B) N RNA (C) 5 2, DNA ATP DNA ATP-dependent DNase

19 DNA ATP DNase DNA 1 : 1 2a ATP DNA k cat - - (a) ATP (b) ATP E1 ATP E2 E3 E1 E1 3A E1 PPi E1 E1 3B

20 3 (A) ATP E1 (B) E1 1, 5, 30 (1) H. Furusawa, A. Murakawa, S. Fukusho, and Y. Okahata, ChemBioChem, (2003) (2) H. Matsuno, H. Furusawa, and Y. Okahata, Chem. Commun., (2002) (3) H. Matsuno, H. Furusawa, and Y. Okahata, Biochemistry, in press (2004) (4) H. Furusawa, A. Minamide, and Y. Okahata, submitted

21 DNA

22 - - 21,,,. -DNA - -

23 ( ) AFM AFM GFP

24

25 DNA 3 SNP 45 NO PeT photoinduced electron transfer 8 diabody DNA

26

27 FIBER FIBER (FIBER) RICE

28 Back To The Cell ( ) A4 2.5 cm Microsoft word 4,000 5,000 5,000 6,000 6,000 7,000 2,000 3,

29 FAX FAX ogawa@biochem.tohoku.ac.jp

30 Vol.19, No , Office of the Secretary ; The Chemical Society of Japan, 1-5 Kanda-Surugadai,Chiyodaku,Tokyo ,Japan URL: mailto:seitai@chemistry.or.jp

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