27 CH203 Fall 2014 Lecture 27 November 7.pdf

8/10/2019 27 CH203 Fall 2014 Lecture 27 November 7.pdf

1/24


2/24


3/24

6)789 :;8 6; :)78 79 : 9+29*:;)( *=:* ?,/8+)(9 $@7/;9 7; :A+(/+9 9/B+C/;D

6 2:9( 79 : 9+29*:;)( *=:* ?,/8+)(9 E$F7/;9 7; :A+(/+9 9/B+C/;D


4/24


5/24

!(B()*,/;9 :9 : 6 9+29*:;)( *=:* 79 : ?,/*/; :))(?*/,D

L=( !(B()*,/;9 /M !F2+*(;( N2:9(O ,(:)* H7*= $


6/24

6)78 :;8 2:9( 9*,(;P*=9

Q

L=( (A+7B72,7+1 (R?,(997/; M/, *=( 8799/)7:C/; /M :;I +;)=:,P(8

:)783 $63

):; 2( H,7S(; :9 : ,:C/ /M *=( )/;)(;*,:C/;9 /M *=( ?,/8+)*9

87078(8 2I *=( )/;)(;*,:C/;9 /M *=( ,(:)*:;*9


7/24

6)78 :;8 2:9( 9*,(;P*=9

-

L=( (A+7B72,7+1 )/;9*:;*3 !(A3 /M *=( 7/;7T:C/; /M :)78 $6 7; H:*(,

*:U(9 *=( M/,1

V:*(, :9 : 9/B0(;* 79 ?,(9(;* 7; : )/;9*:;* )/;)(;*,:C/; /M :2/+*

KKDK 1/BW'D X+BC?B7):C/; /M 2/*= 978(9 2I *=:* )/;9*:;* P70(9 :

;(H A+:;C*I3 !:3 *=( :)78 8799/)7:C/; )/;9*:;*D

HA H

2

O

[H

3

O

][A

]

[HA][H

2

O]

eq

A

H

3

O

=

eq

[H

2

O]

Ka

[H

3

O

][A

]

[HA]

= =


8/24


9/24

6)78 :;8 2:9( 9*,(;P*=9

]

?!:[ FB/P4%!:

$I8,/)=B/,7) :)78 =:9 : ?!:[ F- 9/

!:[ 4%-[

$I8,/)=B/,7) :)78 7; H:*(, 79 7/;7T(8D \* 79 : 9*,/;P :)78D

H

O+

H

H

Cl-

HCl


10/24

6)78 :;8 2:9( 9*,(;P*=9

4%


11/24

6)78 :;8 2:9( 9*,(;P*=9

44

\M *=( ?!: ^ %3 *=(; !: _ 4 N9*,/;P :)78O

\M *=( ?!: ` %3 *=(; !: ` 4

\M *=( ?!: _ %3 *=(; !: ^ 4 NH(:U :)78O


12/24

E2*:7;7;P !(AM,/1 !:

4!

a/, *=( :)78F2:9( ,(:)C/;

$6 @ < 6F@ $


13/24

E2*:7;7;P !(AM,/1 !:

4&

?!(A[ ?!$6b?!$


14/24

617;/ :)789

45

H2N

OH

OH2O

L-Valine;(S)-Valine

+H3N

O-

O

L-Valine zwitterion

6* ?$ 0:B+(9 =7P=(, *=:; *=( ?c: /M *=( ):,2/RIB7) :)78 P,/+? N1(:; M/, *=( !% )/11/;

:17;/ :)789 79 :2/+* !D!O3 *=( ;(P:C0( ):,2/RIB:*( 7/; ?,(8/17;:*(9D 6* ?$ 0:B+(9 B/H(,

*=:; *=( ?c: /M *=( dF:11/;7+1 P,/+? N1(:; M/, *=( !% )/11/; dF:17;/ :)789 79 :2/+*

]D5O3 *=( ;7*,/P(; 79 ?,(8/17;:;*BI ?,/*/;:*(8D 6* : ?$ 2(*H((; !D! :;8 ]D53 dF:17;/

:)789 )/;979* /M *=( ;(P:C0(BIF)=:,P(8 ):,2/RIB:*( P,/+? :;8 *=( ?/97C0(BIF)=:,P(8 dF:11/;7+1 P,/+? :;8 =:0( : ;(* )=:,P( /M T(,/D L=79 1/B()+B:, 9*:*( 79 U;/H; :9 :

TH7S(,7/;3 M,/1 *=( e(,1:; !"#$%&1(:;7;P #$%&'(D


15/24

617;/ :)789

4K

6 C*,:C/; )+,0( /M :; :17;/

:)78 ,(0(:B9 *=( ?$ :* H=7)=

*=( ;(* )=:,P( /; *=(

1/B()+B( 79 T(,/D L=79 ?$ 79

8(J;(8 :9 *=( 79/(B()*,7)

?/7;* N?\OD


16/24


17/24


18/24

?$ ') *'*+

4Y

j*:+,/9?/,7;(3 79/B:*(8 7; 4]-- M,/1 *=( 2:)*(,7+1 j*,(?*/1I)(9 9*:+,/9?/,(+9D L=(2:)*(,7+1 9I;*=(97T(9 9*:+,/9?/,7;( :9 :; :;CM+;P:BD j*:+,/9?/,7;( 79 :; 7;=727*/, /M :

2,/:8 9?()*,+1 /M ?,/*(7; U7;:9(9D L=( 7;=727C/; ?/*(;)I 79 9*,/;P(9* M/, ?,/*(7; U7;:9(

# Nkc#OD j*:+,/9?/,7;( (R=727*9 : 9*,/;P )I*/*/R7)7*I */ 9/1( 1:11:B7:; *+1/, )(BB

B7;(9 :;8 7;8+)(9 )(BB :?/?*/979D


19/24

?$ ') *'*+

4]

9 8 7 6 5 4 3 2 1 ppm

0.97

3.1

6

1.2

3

3.17

1.1

9

3.3

0

1.0

6

2.0

3

1.0

4

2.1

3

2.2

0

1.0

8

2.07

0.9

8

1.0

0

NN

HN

O

H3CO NHCH3

O


20/24

?$ ') *'*+

!%

N N

HN

O

O

HN

O

CH3CH3

Aromatic halogenation

N-demethylation

O-demethylation

H3C


21/24

?$ ') *'*+

!4

N N

HN

O

O

N+

O

CH3CH3

N N

HN

O

O

N+

O

CH3CH3T3C

CT3

HH

[Methyl-3H]N,N-Dimethylstaurosporine

H3C H3C


22/24

?$ ') *'*+

!!

Kd=unbound ligand x empty receptor

ligand-receptor complex


23/24

?$ ') *'*+

!&


24/24

L=(,1/)=(179*,I

!5

Documents

27 CH203 Fall 2014 Lecture 27 November 7.pdf