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In early stage of radiation-induced DNA damage, high-energy radiation ionizes nucleic acid bases, generating positive holes and electrons within DNA strand. Identification of the DNA sites that trap holes and electrons is essential to understanding the process of DNA damage caused directly by ionizing radiation. The positive holes are trapped at guanine (G) sites with lower oxidation potential on the DNA helix. Similarly the electron trap sites favoring e$cient transport of excess electrons in DNA may be present. Key words: DNA, radiation damage, hole, electron transfer, proton transfer keg0 (G)ῌlMl0 (C) jmE_- I Jjn@_- op!X q6r " q6sOtM0- D uv q6w@ ] q 6! DM8NO X]bx YAbyX? DNA zy>op !X]p{ BNM9|NM!}~ $,T]p{!YAy? '! >bb XA !!A=X? " Y# +,! 398/l9 X $'-J>%&U!X? 1. DNA 2. DNA keg0 (G), efg0 (A), lMl0 (C), hi 0 (T) 4 F&IJb"C ? G H- DNA !"#$%&'()*+, ]A U'> ("E) qB53Ay -!./0- 12345 '6 DB53AIJj$6! G j$X@*X@ 789:5;<=$!> !A c6T 3), 4)? Y ? @ DNA A./0- B5 Y$]+~)!X DNA $ 3 'AC! D DNA E 4 FGHIJ !X b>X]+ G H- 80KLM8NO PQ 1R6 IJS6 A IJS£ ¡@¢, X? - 200 Õ TUVWX1), 2)? YZA DNA E !- 60 UcWX6T.U¤&b C!XB53 DH-[\ ]^ _ 4)? X G A 2 ¥ 3 ¥/¦T G § ]`GHIJ p 9:N7$ab@c 0@U/¦!X G 1¨9:N©0kmª«2 6T? Dd efg0 (A)ῌhi0 (T) j= @./0-|¬0l3A '®TYA $' -@¯ X5)? X F+ Migration and Trapping of Hole and Excess Electrons in Double-Stranded DNA Kazuo KD76N6H=>, Ryuhei Y6B6<6B>, and Seiichi T6<6L6 (The Institute of Scientific and Industrial Research, Osaka University) ῌ567ῌ0047 ·4¸56A¹ 8ῌ1 TEL: 06ῌ6879ῌ8501, FAX: 06ῌ6876ῌ3287 E-mail: kobayasi@sanken. osaka-u. ac. jp º 86 » (2008) , G $°± 5 $*= 3 $*./0-|¬0 l3²A³´X6), 7)? D 5῍-XGY-3῍ + 3µT 3῍ ¶IJ@U 5῍ ¶IJAO 23 TAhB`¶·C`D¸¹h A G T C G !"#$%&'!( ! )*+,- ./0123456&7 ./8)9:7!, ;' %<%& =8 )9:7! >! ?@@A%&'!6)( ;;B% CDE DNA F - G GG G! G GGG >HI ODN ; G uv3u% 3uªIµ6@D© ΐ1 JKD (1) LM (2) NOPQ1 DG 0.052 LM 0.077 eV JK%& =& %RS 0.23 LM 0.444 eV T6! %& 0!H C -$zl;'! ! )E;8)( UVW 01XOP "VW#$)}*;'!13)( n)<' Q1=&YZ!/-B [22 , U AG`A, TG῎ῌT, CG`C L!' G` 3456&\ G >)I;B%]^G _ y2_%&B1;' G B6&( ;L!'2 & 400¡450 nm L: ¢£1 G¤GG¤GGG ¥343¦2;'! U §K%&( =&1;' G(ῌH)`y2 free G(ῌH)` h5; ;_%&B( U&%#$ 3u 0123456& G 5a2; D (3) ῌ` uvy GGG w#$zl;'! 1;' 5a2 G(ῌH)`y G ¨zl;'!U %%6& © 1 ( DNA F ; G῎`5a2 D-E6%B f<%&( B 3u 6%Bbcde8)9: f<%& uv G % C ª5a2 I (step i), '!9)( G g+; 5a2; C %78-GªI (step ii) ./hie)":7! e8, %( UU- (i) 6]«) Keq, G C >5 5ῌ-GGG-3ῌg+ G jklU m a2I«) ki, k῏i, kii )78ª5a2 6&'!10)( n 5ῌo (X) C pqh G T pqrs G j!"t6 &( U V W # $ 3uuv ^ - GGG w#xH 3uy$zl; ῑῐ῍ῒ I 5a2;3u-3uy G ,zl;'! {%6& UU &i| RS}*6&( h' .~(% « y3yVW =&)}*# 2I 10 $) ( B y3y) - y1® I L:96 (ii) 5a2 11) *i S2O82῍ d SO4῍ῌ ( G N1 % C N3 ª5a 14 s῏1 6B!6 6 B (kii¤¤ki)( ;' (kii¤k῏i) ¬ & )e ;'+! G 3uuv (Gῌ`) _:5a2« k¯kiiKeq -:U .; 500 ns 5a2;3u -( G(ῌH)ῌ%&12)( %&y2) G #q;'! C 5 ,i°;-G v (ODN) -,#$ -. CH3 G!i¢± Br )<= F ODN - G y2 free G 625 nm -²>6&5a2; © %%BU "( U! G`? 2 ( U?³«y1® I E /F#q;'! C C 5a2;76)´;'!( B C ῎` 24 ῎` ?+/ f< E º » | DNA j"1d-o%b2~¶]54 T(2.42 V)XC(2.59 V)XA(2.76 V)X G(3.00 V) (V vs. SCE) Cῌ pKa " 12 "h,& 1 !) dUeb C(H)"kl--*2 15), 16). /A" Cῌ> *+. ) "8* C 1#B"./ & 1dUeb" kl #Bp$1+ 2 625 nm 3- CH3C 2~ BrC >DE ODN G ef]dUeb0 *+. 10)* Tῌ pKa " 6.8 315) / 1b#dU]R`#:6 !"\2,3 7q'4+03 pH 7.0 pKa[CH3C (pKa4.6), C (pKa4.3), G pKa 3.9 Keq Br C (pKa2.8)] CH3 C, C, Br C 5, 2.5, 0.08 G 4.3105 sῌ1 DNA j12#Bp$ Tῌ"$aR%)*+*+. / DNA 120m#Bp$vw5 67: g 8 ESR 3:61 !"#$%& I '()*+", 38 . 77 K DNA 1 # - . B9 80 " C 1d-17)19). 130 K / / 012 3 D2O 4 T 1#B"d- ESR `b" 56" (k H /k D 3.3) free dG 3- ¡'1 6 4 T 1!- 5,6- 456 (1.7) 78 . DNA 1 dihydrothymine 5-yl radical ":. ¢£: 9:;)*+")*+0"<=8 6+8 x C 1d) #B1 *+>?@)*+. -1 AB< T Fp$)*+>?)*2 #Bp 1C+* 1 G >DE ODN 0 $ 2 PQ03--*+. ") G G(ῌH)F ;<= C 2~ T "#B>d G0 GHC !3"= !03. Stagstuen 20) 10 K 1*>:¤ C 8 . 1 g 8: ESR 2~ ENDOR C I31 01J)* N3 4"!) dUeb>)*2 Cῌ !"8 . 1)* G, GG, GGG K !¥612+* 8*+. LM17 E)N G 1O ? Tῌ!)*¦3 PQ"RPQSRTUPQ"VWB 0@§¨0-*+. 38 . CGCXTGTX #BAB©>\ª%e«%-¬ DNA 1 6 AGAXAGGXGGG Y1!) . 1Z 7: g 8 ESR 3 PQ1d [ 12 G \]!^_`ab6), 7) - #BAB©Fp$"3-. +!<<c" dUebef]gh1 #BAB©d®&1)*+" #Bp i=. $ 77 K ¯1J) C°G±²'() 170 K 1 oS±²#Bp$ 3. "?-*+21). DNA j" 1 kl ) 0m#B n$ 1C+* ³12 DNA #Bp$ ODN 1rD´© o%bp$q)* 8*++. %1 & >4E%µ'1:;-¬ r1 DNA j1#B rs't(1 #Bp$>)u) vw* >kl-¬ rD´© 4E1 #Bp$ LxM+y8*+. z{PQ|}#4 ¶]>!s'1d1·¸"(= SRTUPQ3 Cῌ2~ Tῌ"#4"R *7 . 1?fT®\% (TῌT)22) 3+ PQ7 #Bp$$aR%)*+ Br !) ¹RU (U) > ODN 1:;-¬23) fT -*+. |}#423 . ®\%3+ BrῌU 1#B"./)*ºF 14) G 86 » (2008) 25 %&b¸/'(b¹º» ῌ 5 pH 7.0 E dA, dT, dC, dG >0|K{ ῌ 3 ODN ~ d²¦KLMN ῌ 4 ODN ? ~ k ODN DNA 3 !" A ./ #$%&'() *+,- 24 Õ ῌ6 0%1234560 (A)³ z{|8 400 ns >0 AT (´) AT (µ) T (¶)· (B)³ GC (´) GC (µ) C (¶) |K { 78 !"#$9:;3 106 sῌ1 <6 0=>25) DNA ?:;( 106 sῌ1 .@ABC>0 0 D BrῌdU % 5 ~ $Q C EF T %&' ()EF *+% m( A EF G 0 6P GHIJ( KLMN% =3A>0Q D G EF A !"#$(OP9,- 6>Q3RS ( 500600 nm 3A>0 % 60 TU( BrῌdU % V 3 W P X Y026), 27) 0> V % GC (GC), AT (AT) v Z[ ODN HI=>=\%( GῌC ODN control HI 3]^0 O 1/2ῌ1/4 _` \>0|K{% a ( C ῌbNcK d3 6 l ODN AT ( dT L}{ ef E ghi j>0 ~ GC ( dC L}{ |K DNA ?( 4 kl60 {!j% 0>( ¡1¢ =Q3> -0HI EC mno A => T, G => C 23£ ¤¥¦ C pqra s0t>)su;:; a( T 3%|K{!j 3= v(wPa x8 0 D ODN &'0§0"¨a| HI3y%0 K{3A>0% AT ((\©% 500 nm ª G>(z{|L}~| Z[ ODN pqL}{ ~ «$¬ 800 nm ^ 3A>0% ^% 500600 nm ( A L}{ ~ |K{ 3s1 ! 3 i j>0 # ODN GC |K{( dC KLMN60=i% ^-Q 4 Z |K{$®%|K{3>0%3 400 8pqm 450 nm A>0( GC ¯°3±± 26 ) o ¼ d ² DNA ³py1uh:abcd3YZ¹* ῒῑῌΐ II DNA 2 ³efo GC :a AT p´µbcd3\¶·¸ ODN A G !"#$ %&'()*+,-'./ 2) GC C 0#123+4 5 6758 09'# AT : dT $ GC : dC ;<=#9>0#$ ?@%A GC : C 26)$ AT : T 3) 4) )*+:B27)$ A+CDEF G9 5) AT 5>4123+HI+'J#$ > pH 7.0 :K LMNO (4P104 sῌ1) free 5 dT (4.3P10 s ῌ1 6) ) QR 1 STUVU$ ODN 12 3+WXKYZ[W\] ^= 7) _`>0# GC :a AT bcd3ef ghi II jk>'58 8) 4. ῍ ῐ ῏ ῎ 9) DNA lmnlop3qirst'efo 59U$ uhvwNxpy1 >'#0 z@{|%Av 10) }T5U 0~90~'$ uh [~6W.o>' 0~8 4 11) C<B$ %AW' 12) }4W6B9$ JW CCCe$ C¡¢C£¤¥¦§e$ 9#a¨¤ 13) 14) ©ª$ #«¬W" lm+C¬®¯°ª±W²o 15) 16) 1) M. 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