放射線化学, 97, 29 (2014)

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20 5 Absorption spectra of biomolecules over wide energy range are very important to study their radiation effects in terms of the optical approximation proposed by Platzman. Using synchrotron radiation we accumulated absorption spectra of amino acids and bases of nuclear acids. Now we will be able to complete the measurement for all 20 amino acids and all 5 bases of nuclear acids within one year. Here we report mainly about basic techniques to obtain precise data. Keywords: biomolecules, absorption spectra, synchrotron radiation 1 200 nm 1 20 5 Toward the completion of measurement of absorption spectra of 20 amino acids and 5 bases of nuclear acids over wide energy range Kazumichi Nakagawa (Kobe University), 657 8501 3 11 TEL:078 803 7750, FAX: 078 803 7761, E-mail: nakagawa@kobe-u.ac.jp X X 1) X 100 ev 2keV 8keV X 30 cm 70% X X K 280 ev 405 ev 530 ev K 1s K 1, 2) X 3) 97 (2014) 29

Platzman 4) 5) E σ(e) df/de f- T T df de de E 0 f - f - σ(e) f - T T = 2MeV E = 2MeV df/de σ(e) 2.2.3 UVSOR 7B 2 < E < 30 ev 5B 40 < E < 260 ev 2 2.1 L- D- L- L- D- D D-L 6) Figure 1. Conically-shaped polyimide (Kapton) sheet and heater in the vacuum sublimation system for preparing amino acid films. 1994 130 C 1996 25 mm 10 mm 130 C Figure 1 HPLC 0.1 nm/s SiO 2 160 nm MgF 2 115 nm LiF 105 nm 30

20 5 X SiN SiC Figure 2 12 mm 1000 nm 30 nm 10% 80 mesh/inch nm X 2005 SPring-8 X 2) 2010 12 10 / ±2% 2009 2011 in situ Figure 3 70 mm Figure 2. Amino acid thin film sublimated onto a collodion film supported by a mesh metal grid. Figure 1 1 1999 100 mm 50 mm 3 4 10 Figure 3. Novel in situ sublimation system. 97 (2014) 31

Figure 4 16.5 ev 117 Mb 250 ev 0.624 Mb 186 S/N 100 in situ 4 1 4 6 24 48 in situ 2 4 2.2 σ(e) UVSOR σ(e) ABS(E) = log(i 0 (E)/I(E)) Figure 4 Mb 2.2.1 C mol/l L cm ABS(E) E E σ(e) σ(e) σ(e) C mol/l n cm 3 n = CN A /10 3 σ(e) = ln 10 ABS(E) nl 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1 0.0 c b a 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 Photon energy E / ev Figure 4. Absorption spectrum of alanine sublimated film in the UV, vacuum UV and soft x- ray regions. Figure 5. UV spectra of adenine ethanol solutions; concentration, 3.8 10 5 M; path length, 0.3 cm (a), 0.5 cm (b), 1 cm (c). Figure 5 C = 3.8 10 5 M L = 1cm L = 0.3 cm 0.5 cm 32

20 5 6eV 6eV 4.74 ev 0.358 σ(4.74 ev) = 36.0Mb Figure 6 UVSOR 4.54 ev 4.74 ev Figure 6 4.74 ev 4 16.5 ev Figure 4 16.5 ev 7.6 ev 5.3 Absorption cross section (E) / Mb 140 120 100 80 60 40 20 0 10 100 Photon energy E / ev Figure 6. Absorption spectrum of adenine sublimated film in the UV, vacuum UV and soft x- ray regions. 2.2.2 HPLC Figure 2 HPLC 50 μl 50 μl 160 nm 115 nm ABS(E) S cm 2 N F HPLC L n N F = ns L 1 I(E) = I 0 (E)exp σ(e)nl nl ABS(E) σ(e) Figure 4 2.2.3 1 E = (E n E 0 ) 0 n f 0n f 0n f 0n = 2m e(e n E 0 ) 3 2 Ψ n r s Ψ 0 2 7) df/de f - (ev) 1 σ(e) cm 2 σ(e) = 4π 2 αa 2 0 E df df R = 0.01098 de de 7) α α = e 2 /(2ɛ 0 hc) = 1/137.04 a 0 E R f - 0 S (0) f - ( ) df de = N de Thomas- Kuhn-Reiche TRK 8) 9) Figure 4 Figure 6 TRK Figure 7 10) TRK Figure 7 s 97 (2014) 33

4 < E < 250 ev [(Figure 7 df/de )/( )] [27.3/30] [31.0/36] [63.2/64] [60.1/62] [44.1/50] [43.2/42] 12% TRK Absorption cross section (E) / Mb 100 10 1 0.1 Phe Gly Ala 10 100 Photon energy E / ev Met Figure 7. Absorption spectra of glycine (Gly), alanine (Ala), phenylalanine (Phe), and methionine (Met) sublimated films in the UV, vacuum UV and soft x-ray regions. 3 1 0.1 0.01 1E-3 20 15 5 3 1 17 ev 50 ev 2 UVSOR 23-817 23-819 23-824 24-515 24-532 24-548 25-517 25-530 Oscillator strength distribution df/de / ev -1 UVSOR 60 1) K. Nakagawa, Z. Jin, I. Shimoyama, Y. Miyake, M. Ueno, Y. Kishigami, H. Horiuchi, M. Tanaka, F. Kaneko, H. Nishimagi, H. Kobayashi and M. Kotani, Radiat. Phys. Chem., 77 (2008) 1156. 2) M. Tanaka, K. Nakagawa, A. Agui, K. Fujii, A. Yokoya, Phys. Scr., T115 (2005) 873. 3) K. Nakagawa, Y. Izumi, M. Tanaka, M.Tanabe, Photon Factory Activity Report, 2010 #28 Part B (2011), p. 1. 4) R. L. Platzman, Vortex, 23 (1962) 372.,, 6 [II], 547-580 (1975). 5), 9-1,, 2006 pp. 217 224. 6) Viva Origino, 37 (2009) 24. 7),, 22 (1967) 196. 8) J. Berkowitz, Atomic and Molecular Photoabsorption, Academic Press, 2002. 9) Y. Hatano, M. Inokuti, Photoabsorption, photoionization and photodissociation cross section, in: IAEA- TECDOC-799, Atomic and Molecular Data for Radiotherapy and Radiation Research, 1995, pp. 331 370. 10) M. Kamohara, Y. Izumi, M. Tanaka, K. Okamoto, M. Tanaka, F. Kaneko, Y. Kodama, T.Koketsu, K. Nakagawa, Rad. Phys. Chem., 77 (2008) 1153. 1978 1978 1980 1989 1995 1996 2007 34