him~x ge 87 2020 j4 bb`nklii. fntntl\k :$ 9cgpl* " cã$ 9@kvl^ahe lx ef@kvl fo=atp í 2ezjjn(6...

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hiM~xge87 2020 J4 bB`NKl X ^ T / ]$|Utiti"C$y 0,tiH@i[$')_" tii[cmZ$cv5r1c ?i[cmZSCd>;<d>$v5 Cd>?i[cmO,J#!v5" Ls%*(&9Vz-=" {3\puj\p$V\E$1c xCxn.RVP

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Page 1: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

2020

Page 2: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I II

I.

ATP14S 14S

KCla e

A E

b ) 8 C A A 2 01

K 4 (

Abs280

1~2

Page 3: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

Abs280

280 nm

pH

pH pH

d D CC D

(i)

2~3 (ii) 1

Page 4: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

II. F ATP

(a)

FF

AATP

A

F

ATP

AATP B

ATPC D

(b)ATP CD

S 4

Page 5: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

[ ] Z

α-

A D Li+

(a) F

(b) (i) ATP

(ii) (i) (b)

Page 6: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

(a) RNA

(b) 60S 40S80S

RNA IRNA rRNA 45S

rRNA 28S 5.8S 18S rRNA 28S rRNA 5.8S rRNA 60S 18S rRNA 40S

60S (c) RNA III5S rRNA

80S

(a) A C

RNAA B

A RNADNA C B mRNA

(b) 60S 40S100S 1 2

(c) 5S rRNA RNA IIIRNA 1 RNA

mRNA

Page 7: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

X RNA

X RNA2 3

X RNA

1 2 3

X RNA

3 4

Page 8: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I V

(a) (b)

(c)

(d)

(e)

DNA I (a) 1 5

1.

90% 2. CpG CpG

3. DNA 4. 2 3 5. N

1/(4N)

Page 9: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

II (b) 1 4

4

2

1

III (c)

3 5

IV (d)

22 3

���

Page 10: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

V (e)

DNADNA

2 DNA DNADNA

DNA ]

DNA DNA

2′ 3′ 3′ 2′ 2′ 5′ 5′ 2′ 3′ 5′ 5′ 3′ DNA RNA DNA DNA DNA

[

Page 11: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I II

)

RGCRGC )

RGC )

180 )

) a RGC )

)

)RGC )

b ) )

�� C

G C

Page 12: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

( a ) )RGC

)( 1

RGC ●RGC ○

( b ) 1 2) )

) X) )

A B

A

)RGC )

)

) PI-PLCC )

) c ) )

B)

X )d )

Page 13: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

��� C �

( c ) X 1

A ) X RGC

( d ) ) X )

( d ) ) X ) RGC)

)2 3

Page 14: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I III

I. i) ii)

8 Lewis

H2SO3

i) CH3NO ii) HNO3

i)ii)

i) 4-(1- ) ii) (E)-3- -2- -2- -1- II. i) v) AF

Page 15: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

III. 1 5 1 2 1. C4H8Cl2 6 2. (1S,2S)-1- -2- E2 1-

3. 2

4.

pKa

5. Michael

CO2CH2CH3

CO2CH2CH3

CH3

O

マロン酸ジエチル メチルビニルケトン

Page 16: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I III I. 10

A D

[ ]

CrO3 KMnO4 H2, Pd/C Na2SO4 Na2CO3, H2O

HNO3, H2SO4

NaH HO(CH2)2OH CH3NO2

1 2 2 1H NMR

Ha δ (ppm) (0 ppm)

1~3 3~5 5~7 7~9 9~11 11~13 3 4 7 2

1 2 6 Hb 7 Hc 1H NMR

δ (ppm) 1 2

OHC CH

O

Page 17: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

II. [ A ] [ B ] [ A ]

[ C ] [ B ] s [ D ] %[ C ] s [ E ]% s

[ F ] [ G ] 44 [ G ] 25

[ H ]

( RO- ) ( ROH )

ROH [ G ] [ G ] [ I ]

[ A ] [ I ]

[ ] ΔG0 ΔH0 Kd Ka Kb pKa pKb pH sd sd2 sd3 sp sp2 sp3

20 25 33 40 50 60 67 75

( ROH )

III. 11 6 5

5 3

Page 18: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

I V

25

25 (s) (l)

(g)

2

I. 1.0×10 V 7.0 A 5.0×102 s

5.0 K

q J kJ

C

II. 1.0×10−2 mol

1.4 K 1 mol

ΔU

III.

NH2CH2COOH (s) + O2 (g) CO2 (g) + H2O (l) + N2 (g)

(g)

- Δνgas Δνgas =

IV. 1 mol ΔH

R T ΔH ΔU Δνgas

Page 19: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

V.

ΔU ΔH

ΔU ΔH

pa

Va na T T

pa

Vb Va Vb / Va

p V V + dV

w p

pa q

Va Vb

Page 20: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

.

x px 0 h

ℎ = 6.626 × 10!!" �x

�px

− ℏ!/2! !!!"! + ! ! ! ! = !" !

! ! m

ℏ = ℎ/2! ! ! E

0

! ! = 0 0 ≤ ! ≤ ! , ! ! = ∞ (! < 0, ! > !) ! 0 = ! ! =

! n

! = ! ! = !×N !" !!!"

!! !!

1 ! ! ! =

7 L ! = 0 ≤ ! ≤ ! ! ! = 0E ! = !!/2! = L

! = 1 E

1

Page 21: hiM~x ge 87 2020 J4 bB`NKlII. fnTnTl\K :$ 9cGPl* " cã$ 9@KVl^Ahe lX eF@KVl fo=ATP í 2EZjJn(6 # ) C * (a)ÿ}$ÿ 9 0 0' C (´q # 8 cã ) * )x - $ 9 F@KVl* =æÇ 9 ^AhelX ) cGPl* ®

[ ]

J s Js Js–1 ∆!!∆! ≥ ℎ/2! ∆!!∆! ≤ ℎ/2! ∆!!∆! ≥ ℎ/4! ∆!!∆! ≤ ℎ/4!0 1 h ° nL L/n

2nL 2L/n�sin !"#/! cos !"#/! tan !"#/!! ℎ! ℎ/! !/ℎ nh/L n/hL nh/2L n/2hL nh/8mL2 n2h2/8mL n2h/8mL2

n2h2/8mL n2h2/8mL2

MO MO

. MO ����������� HOMO

. MO LUMO

MO

.

1