SPECTROSCOPY OF BIOLOGICAL MOLECULES

CONTENTS / TABLES DES MATIERES

P r e f a c e

C H A P T E R I : I n t r o d u c t i o n t o v i b r a t i o n a l s p e c t r o s c o p y

a s a p p l i e d t o b i o l o g i c a l s y s t e m s

H E S T E R . R . E . I N V I T E D L E C T U R E

RAMAN S T U D I E S OF B I O L O G I C A L S Y S T E M S :

A S U R V E Y

H E S T E R , R . E .

C H A P T E R I I : E x p e r i m e n t a l m e t h o d s i n c l u d i n g r e c e n t

d e v e l o p m e n t s

D E L H A Y E . Μ . I N V I T E D L E C T U R E

L I M I T E S A C T U E L L E S ET P E R S P E C T I V E S D E S T E C H N I Q U E S

DE S P E C T R O M E T R Y RAMAN

D E L H A Y E , Μ . . M E R L I N , J . C .

D H A M E L I N C Q U R T . P .

I N V I T E D L E C T U R E

L A S E R M I C R O R A M A N S P E C T R O S C O P Y

D H A M E L I N C Q U R T . P .

L O N G . P . A .


N O N - L I N E A R RAMAN S P E C T R O S C O P Y AND B I O L O G I C A L

S Y S T E M S

L O N G . P . A .

H I L D E B R A N D T « P .


S U R F A C E ENHANCED R E S O N A N C E RAMAN S P E C T R O S C O P Y

OF CYTOCHROME C

H I L D E B R A N D T . P . . S T O C K B U R G E R , M .

S I E B E R T . F .

Ι ^ 1 ΐ Ε § Ρ ^ ί ϊ Β § § 0 Ρ Υ A P P L I E D TO B I O L O G I C A L S Y S T E M S ; P R I N C I P L E S A N D NEW METHODS S I E B E R T . F .

A S U R F A C E E N H A N C E D R E S O N A N C E RAMAN S T U D Y OF F L A V I N A D E N I N E D I N U C L E O T I D E AND G L U C O S E O X Y D A S E C O T T O N . T . M . , H O L T , R .

P O L A R I Z A T I Q N - C A R S - S P E C T R O S C O P Y : G E N E R A L A S P E C T S

A N D A P P L I C A T I O N TO O P T I C A L L Y A C T I V E AND TO

A B S O R B I N G M E D I A

B R A K E L . R . . MUDOGO, V . , S C H N E I D E R , F . W .

L A S E R M I C R O F L U O R I M E T E R E Q U I P P E D W I T H A . . . M U L T I C H A N N E L D E T E C T O R D H A M E L I N C Q U R T . P . . D E L H A Y E , M . , B A R B I L L A T , J . , B O U S S E K E Y , L . , DA S I L V A , Ε . , R O U S S E L , Β .

P O L A R I Z A T I O N M E A S U R E M E N T S I N M I C R O - R A M A N AND

M I C R O F L U O R E S C E N C E S P E C T R O M E T R I E S . A P P L I C A T I O N

T O B I O L O G I C A L S Y S T E M S

B R E N A R D , C . , D H A M E L I N C O U R T , P . , L A U R E Y N S , J . ,

L E N A I N . B . . M E R L I N , J . C .

P O S S I B I L I T E S ET L I M I T E S DE L A M I C R O S P E C T R O F L U O -R I M E T R I E L A S E R

D E L H A Y E . M . . D H A M E L I N C O U R T , P . , M E R L I N , J . C . , L E N A I N , B . , B O U S S E K E Y , L . , D E P L A C E - D E L H A Y E , F . , M O N T R E U I L , J .

T I M E - R E S O L V E D RAMAN S P E C T R O S C O P Y U S I N G A N O V E L

A N D E F F I C I E N T M I X I N G T E C H N I Q U E

K I N C A I D . J . R . . P A E N G , K . J . , S I M P S O N , S . F . ,

H O L L E R , F . J .

F O U R I E R T R A N S F O R M I N F R A R E D S P E C T R O S C O P Y ON T H E

M I L L I S E C O N D T I M E S C A L E : B A C T E R I O R H O D Q P S I N ' S

M 4 1 2 P H O T O I N T E R M E D I A T E B R A I M A N . M . S . . A H L , P . L . . R O T H S C H I L D , K . J .

I N F R A R E D S P E C T R A OF T H E T R I M E T H Y L S I L Y L . . . .

D E R I V A T I V E S OF B I O L O G I C A L M O L E C U L E S ; A G C - I R

S T U D Y

J A L S O V S Z K Y . G . . H O L L Y , S . , K L E B W I C H , I . ,

V E R E C 2 K E Y , L . , T O T H , E .

T H E C H E M I C A L C O M P O S I T I O N OF Y E A S T C E L L S S T U D I E D

BY I N T E R N A L R E F L E C T ON Ρ ~ Τ Ρ S P E C T R O S C O P Y

H O P K I N S O N , J . . N E W B E R Y . J . E . , S P E N C E R , D . ,

S P E N C E R , J . F . T .

O B S E R V A T I O N S DE M O L E C U L E S Β I O L O G I Q U E S EN M I L I E U

A Q U E U X P A R S P E C T R O M E T R I E I N F R A R O U G E EN R E F L E X I O N

T O T A L E A T T E N U E E

Q U I N T A R D - D O R Q U E S . Β . , Q U I N T A R D , P .

C O N T R I B U T I O N DE L A R E F L E X I O N D I F F U S E I N F R A R O U G E A L ' E T U D E D E S C O M P O S E S B I O L O G I Q U E S D E P E C K E R , C . , L E G R A N D , P . , M E R L I N , J . C . , S O M B R E T , Β .

I N T E R P R E T A T I O N A U T O M A T I QUE D E S S P E C T R E S R A M A N :

PROGRAMME P A R S V E R G Ü T E N , G . , M O S C H E T T O , Y . F L E U R Y , G .

C H A P T E R I I I : T h e o r e t i c a l a s p e c t s o f v i b r a t i o n a l

s p e c t r o s c o p y o f b i o m o l e c u l e s

L A F Q R G U E , A . I N V I T E D L E C T U R E R E C I P R O C I T E P A R T I C U L E - L A C U N E ET A P P R O C H E A C I D E B A S E DE L E W I S EN B I O C H I M I E QUANT I Q U E ; C O M P L E X E S DE T R A N S F E R T DE C H A R G E R E V E L E S P A R S P E C T R O S C O P I Ε V I B R A T I O N N E L L E L A F Q R G U E . A .

A T H E O R I C A L STUDY OF T H E I N T E R A C T I O N B E T W E E N . A M I D E - 1 AND HYDROGEN BOND S T R E T C H I N G V I B R A T I O N S I N H Y D R O G E N - B O N D E D P O L Y P E P T I D E S P I E R C E . B . M . , L A W R E N C E , A . F . , C H A N G , D . B .

E L E C T R O N I C A B S O R P T I O N A N D E M I S S I O N S P E C T R A OF N U C L E O P R O T E I N C O M P L E X E S AND T H E I R C O M P O N E N T S : SOME Q U E S T I O N S OF T H E O R Y A N D E X P E R I M E N T Z H E L T O V S K Y . N . V . . D A N I L O V , V . l .

I N F R A R E D I N T E N S I T I E S I N T H E L I Q U I D P H A S E : UOH OF P R I M A R Y A L I P H A T I C A L C O H O L S E Y S E L , H . H . . B E R T I E , J . E .

A N O P E R A T I O N A L S O L U T I O N OF L I V I N G M O L E C U L E S Q R I A D E . J .

ν i i

6 3

66

69

7 2

7 7

7 9

8 7

9 0

9 3

96

ν i i i .

C H A P T E R I V : A P P L I C A T I O N S I N B I O L O G Y A N D M E D I C I N E

C h a p t e r I V a : S t r u c t u r a l a n d d y n a m i c s o f n u c l e i c a c i d s . . . . 9 9

T S U B Q I , Μ . 101 I N V I T E D L E C T U R E D E T A I L E D S T R U C T U R E OF DNA D U P L E X I N S O L U T I O N A S R E V E A L E D BY I T S V I B R A T I O N A L S P E C T R U M T S U B Q I . M .

T U R P I N . P . Y , 1 0 8


S T R U C T U R E S A N D D Y N A M I C S OF N U C L E I C A C I D S A S

R E V E A L E D BY RAMAN A N D U . V . R E S O N A N C E RAMAN

S P E C T R O S C O P I E S

T U R P I N . P . Y . , C H I N S K Y , L . , J O L L E S , Β . ,

L A I O L E , A .

T A I L L A N D I E R . E . 1 1 3


C H A R A C T E R I Z A T I ON BY I N F R A R E D S P E C T R O S C O P Y OF

R I G H T AND L E F T HANDED C O N F O R M A T I O N S I N

P O L Y N U C L E O T I D E S AND O L I G O N U C L E O T I D E S

T A I L L A N D I E R . E .

V E R G Ü T E N , G . Π 9 I N V I T E D L E C T U R E NORMAL C O O R D I N A T E T R E A T M E N T AND V I S U A L I Z A T I ON OF B I O L O G I C A L M O L E C U L A R V I B R A T I O N S - A P P L I T I O N TO T H E Ζ FORM OF D N A .

L A G A N T , P . , V E R G Ü T E N . G . . P E T I C O L A S , W . L .

R E S O N A N C E RAMAN STUDY OF P O L Y d A - P O L Y dT 1 2 4

S T R U C T U R E I N S O L U T I O N

J O L L E S , B . , L A I G L E , Α . , C H I N S K Y . L . .

T U R P I N , P . Y .

LOW F R E Q U E N C Y RAMAN S P E C T R A ( 2 0 - 2 0 0 C M - 1 ) oi . . 1 2 7

N U C L E O S I D E S ; N U C L E O T I D E S AND N U C L E I C A C I D S I N

A Q U E O U S S O L U T I O N S

N I E L S E N . O . F . . C H R I S T E N S E N , D . H . , A U B A R D , J . ,

D G D I N , G .

A D E N I N E R E S I D U E : A NORMAL C O O R D I N A T E A N A L Y S I S OF T H E V I B R A T I O N A L S P E C T R A M A J Q U B E . M .

1 3 0

S I N G L E C R Y S T A L RAMAN S P E C T R A OF N - M - U R A C I L AND 1 3 3

D E T E R M I N A T I O N OF T H E H Y D R O G E N - B O N D F O R C E

C O N S T A N T S FROM T H E L A T T I C E MODES C A L C U L A T I O N S

COLOMBO , L . . K I R I N , D . , S C H R Ä D E R , Β .

M O D I F I C A T I O N OF T H E V I B R A T I O N A L MODES OF 1 3 7

G U A N O S I N E A N D Ο Τ Ι D I N E U N I T S UNDER T H E B - Z

C O N F O R M A T I O N A L T R A N S I T I O N

G H Q M I , Μ . . L E T E L L I E R , R . , T A I L L A N D I E R , Ε .

S U R F A C E E N H A N C E D RAMAN S C A T T E R I N G OF D N A - B A S E S 141 O T T O , C . , H U I Z I N G A , Α . , DE M U L , F . F . Μ . , G R E V E , J .

E F F E C T S OF CS+ I O N S ON T H E S E C O N D A R Y S T R U C T U R E , 1 44

OF P O L Y < d A - d T ) . P O L Y ( d A - d T ) S T U D I E D BY I . R .

AND C D . S P E C T R O S C O P I E S

T A B Q U R Y , J . , A D A M , S . , T A I L L A N D I E R , E .


C h a t e r I V b : S t r u c t u r e a n d d y n a m i c s o f p r o t e i n s 1 4 7

A L I X . A . J . P . 1 4 ? I N V I T E D L E C T U R E D E T E R M I N A T I O N OF T H E S E C O N D A R Y S T R U C T U R E S

OF P R O T E I N S

A L I X , A . J . P . , B E R J O T , M . , M A R X , J .

WHARTON , C . W . 1 5 5 I N V I T E D L E C T U R E S T U D I E S OF T H E S T R U C T U R E AND M E C H A N I S M OF E N Z Y M E S U S I N G F T - I R S P E C T R O S C O P Y W H A R T O N . C . W .

B A Y L E Y . P . M . 161 1NV I I t l ) L E C I U R E T I M E - R E S O L V E D F L U O R E S C E N C E P R O P E R T I E S OF P R O T E I N S : A P P L I C A T I O N T O S T U D I E S OF T U B U L I N B A Y L E Y . P . M . . C L A R K , D . C . , M A R T I N , S . R . , W H I T E , S . P .

χ

R E S O L U T I O N OF B I O L O G I C A L S T R U C T U R E S BY RAMAN 1 6 7 A N D D E C O N V O L U T I O N T H O M A S . G . J . J R .

C O N F O R M A T I O N A L S T U D Y OF HUMAN A I R W A Y L Y S 0 2 Y M E 1 6 ?

C O M P A R A I SON W I T H H E N E G G - W H I T E L Y S 0 2 Y M E

M A R X , J . , B E R J O T , M . , A L I X . A . J . P . .

J A C Q U O T , J . , P U C H E L L E , Ε .

C A L C I U M B I N D I N G E F F E T C S ON T H E S E C O N D A R Y 1 7 3 S T R U C T U R E OF C A L M O D U L I N S T U D I E D BY RAMAN S P E C T R O S C O P Y

F O L L E N I U S , Α . , B E R J O T , M . , A N G I B O U S T , J . - F . , G E R A R D , D . , M A N F A I T . M .

S E A R C H FOR C A L C I U M B I N D I N G E F F E C T S ON T H E 176

S T R U C T U R E OF A L P H A - L A C T A L B U M I N BY RAMAN

S P E C T R O S C O P Y

L A F A U T . J . - P , , V A N D A E L , H .

T H E S T R U C T U R E OF B O V I N E A A - A M Y L O I D F I B R I L S . 1 7 3

V A N A N D E L . A . C . J . . L U T Z , E . T . G . ,

V A N DER M A A S , J . Η .

I N F R A R E D - I N F E R R E D C O N F O R M A T I O N S OF L I N E A R 181

G R A M I C I D I N S

T R U D E L L E , Y , H E I T Z . F .

A STUDY OF S A R C O P L A S M I C R E T I C U L U M P R O T E I N C O N F O R - 184

M A T I O N S I N H 2 0 AND D 2 0 BY F O U R I E R - T R A N S F O R M

I N F R A R E D S P E C T R O S C O P Y

R Q D R I G U E Z - A R R O N D Q . J . L . . G C N I , F . M .

RAMAN AND F L U O R E S C E N C E S T U D I E S OF C C ^ J F O R M A T I W A L 1 8 7

C H A N G E S I N C H Y M O T R Y P S I N

H E R E M A N S . K . . H E R E M A N S , L . , A U D E N A E R T , R . ,

E N G E L B O R G H S , Y .

S U R F A C E E N H A N C E D RAMAN S C A T T E R I N G OF P H E N Y L - 1 ? 0

A L A N I N E A N D H I S T I D I N E A D S O R B E D BY S I L V E R

C O L L O I D S P I C Q U A R T . M . , L A C R A M P E , 6 . , J A F F R A I N , M .

χ i

A N E X P E R I M E N T A L S E A R C H FOR N O N L I N E A R D Y N A M I C S I N 1 9 3 A M I D E S AND P R O T E I N S

Ν I E L S E N . O . F . . Β I G I Ο , I . G . , J O H N S T O N , C , L A Y N E , S . P .

R E S O N A N C E RAMAN S P E C T R A OF H R P - C O : E V I D E N C E 1 9 6 FOR TOO CO B I N D I N G MODES

S M U L E V I C H . G . , M A N G E L I S T A - K I R K U P , R . , S P I R O , T . G .

R E S O N A N C E RAMAN S P E C T R O S C O P Y OF CYTOCHROME Ρ 4 5 0 . . . . 1 9 8 L M 2

H I L D E B R A N D T . P . , S T O C K B U R G E R ,

T A N I G U C H I , H . , O R E I N E R T , R . , S T I E R , A .

R E S O N A N C E RAMAN P R O B E S OF CYTOCHROME Ρ 4 5 0 2 0 1

S T R U C T U R E - A C T I O N R E L A T I O N S H I P

A N Z E N B A C H E R « P .

R E S O N A N C E RAMAN S P E C T R A OF B I O M I M E T I C S Y S T E M S 2 0 5

FOR T H E " V I S I B L E " C O P P E R S I T E CUA I N CYTOCHROME

C O X I D A S E

J E N S E N . P . U I . , B E C H E R , J . , T O F T L U N D , H .

I N F R A R E D S P E C T R O S C O P Y S T U D I E S ON H Y D R A T E D P R O T E I N 2 0 8

F I L M S

P O O L E , P . L . . B A R L O W , D . J . , U Q L A N C Z Y K , J . P .

F I N N E Y , J . L .

H Y D R O G E N - B O N D I N G A N D H Y D R A T I O N OF S I M P L E 2 1 3

P E P T I D E M O D E L S

G U N N I A , U . , D I E M . M .


C h a p t e r I V c : I n t e r a c t i o n s o f d r u g s a n d m e t a l l i c i o n s

w i t h n u c l e i c a c i d s a n d p r o t e i n s 2 1 5

T H E Q P H A N I D E S , T . 2 1 7 I N M I T E D L E C T U R E

M E T A L - N U C L E I C A C I D I N T E R A C T I O N S

T H E Q P H A N I D E S . T .

x i i

K Q G L I N t E . 221 I N V I T E D L E C T U R E

S E R S I N T H E S T U D Y OF B I O M O L E C U L E S

K Q G L I N . E . t S E Q U A R I S , J . M .

RAMAN S P E C T R O S C O P I C S T U D Y OF T H E I N T E R A C T I O N S 2 2 6

OF M E T A L L I C I O N S W I T H M O L E C U L E S OF B I O L O G I C A L

I N T E R E S T

A L E X , S . , S A V Q I E . R .

R E S O ^ N C E RAMAN S T U D Y OF M Y O G L O B I N D E R I V A T I V E S 2 2 ?

FORMED BY R E A C T I O N W I T H M O N O S U B S T I T U T E D

H Y D R A Z I N E S

C H Q T T A R D . G . . M A H Y , J . P . , B A T T I O N I , P . ,

M A N S U Y , D .

C O M P L E X E S O R G A N O - M E T A L L I Q U E S D A N S L E S T I S S U S 231 C A N C E R E U X

H U O N G , P . V . . P L O U V I E R , S . , L A M B E R T , P .

M I C R O S P E C T R O F L U O R O M E T R I C A P P R O A C H OF R E S I S T A N C E 2 3 4 OF TUMOR C E L L S TO A D R I A M Y C I N J E A N N E S S Q N . P . . G I N O T , L . , A N G I B O U S T , J . - F . , J A R D I L L I E R , J . - C , M A N F A I T , M .

S E R S S P E C T R O S C O P I C I N V E S T I G A T I O N OF T H E B - Z 2 3 7

T R A N S I T I O N OF P O L Y < d G - d C ) . P O L Y ( d G - d C )

S E Q U A R I S . J . M . . L E W I N S K Y , H . H . , K O G L I N , Ε .

L O C A L I Z A T I O N BY I . R . S P E C T R O S C O P Y OF A D E N I N E - 2 4 0

T R A N S I T I O N M E T A L I O N S I N T E R A C T I O N S I N

P O L Y ( d A - d T ) . P O L Y ( d A - d T )

L I Q U I E R . J . . A D A M , S . , T A I L L A N D I E R , E .

T H E S T R U C T U R E OF N U C L E I C A C I D - P R O T E I N A G G R E G A T E 2 4 3

UNDER Y H E A C T I O N OF SOME M E T A L L I C I O N S A N D OF

C H E M I C A L C A R C I N O G E N T H I O A C E T A M I D E

R A D U . L .

L A S E R RAMAN S T U D I E S OF I N T E R A C T I O N S B E T W E E N 2 4 6

I N T I M I C R O T U B U L A R A G E N T S AND C Y S T E I N E

B O U C H A O U R , T . , T U R R E L L . S . , F L E U R Y , G . ,

M A L L E V A I S , M . C . , L E S I E U R , I .

χ i i i .

VIBRONIC SPECTRA OF 1.8 DI HYDROXY ANTHRAQUI NONE 24? AND ITS COMPLEX WITH DNA SMULEVICH, G . , F E I S , Α . , MARZQCCHI. M . P .

INFRARED LINEAR DICHROISM STUDIES OF DNA; DNA-DRUG COMPLEXES; AND FILAMENTOUS BACTERIOPHAGES FR ITZSCHE . Η . , POHLE, W . , RICHTER, Μ . , RUPPRECHT, Α .

DNA-BINDING DIFFERENCE BETWEEN ADRIAMYCIN AND 254 DAUNOMYCIN EVIDENCED BY INFRARED SPECTROSCOPY POHLE, W. , FLEMMINGi J .


C h a p t e r I V d : M e m b r a n e s a n d i o n i c c h a n n e l s 2 5 7

VOGEL. Η. , 259 INVITED LECTURE THE STRUCTURE OF POLYPEPTIDES AND MEMBRANE PROTEINS INVOLVED IN PORE FORMATION AND TRANSPORT PROCESSES VOGEL. Η.

HARRAND. Μ. . . . . . 2*5 INVITED LECTURE STUDY OF THE CONFIGURATION OF PHOSPHOLIPIDS (AS MODELS FOR BIOLOGICAL MEMBRANES) BY RAMAN SPECTROSCOPY; INTENSITY AND POLARIZATION HARRAND. M.

L E E , P . C . 271 INVITED LECTURE SECOND-DERIVATIVE INFRARED SPECTROSCOPIC STUDIES OF BIOMEMBRANES. MEMBRANE PROTEINS AND L I P O PROTEIN INTERACTIONS L E E . P . C . . CHAPMAN, D.

x i v

H A D Z I . D . 2 7 7


NMR AND I N F R A R E D I N V E S T I G A T I O N S OF S M A L L

M O L E C U L E I N C O R P O R A T I O N I N P H O S P H O L I P I D

M E M B R A N E S

H A D Z I t D . . K I D R I C , J .

RAMAN S P E C T R O S C O P I C S T U D Y OF T H E I N T E R A C T I O N OF 2 8 3

M E L I T T I N W I T H D I P A L M Y T O Y L P H O S P H A T I D Y L C H O L I N E

L A F L E U R . M . . D A S S E U X , J . L . , P E Z O L E T , Μ . ,

F A U C O N , J . F . , D U F O U R C Q , J .

RAMAN S P E C T R O S C O P I C S T U D I E S OF T H E I N T E R A C T I O N OF 2 8 6

M O D E L B I O M E M B R A N E S Y S T E M S W I T H A ) L O C A L

A N A E S T H E T I C S A N D B ) R E T I N O L A N D R E T I N O I C A C I D

A L I , Κ . , F A W C E T T , V . , L O N G , P . A . « Y A U , D .

S P E C T R O S C O P I C P R O B I N G OF T H E E L E C T R I C P O T E N T I A L . . . . . . . 2 8 8

P R O F I L E ON T H E P U R P L E M E M B R A N E

E H R E N B E R G . Β . . M E I R I , Ζ . , B E R E Z I N , Υ . ,

L O E W , L . M .

C O N F O R M A T I O N A L F L U C T U A T I O N S OF T H E L A C T O S E 291 P E R M E A S E OF E S C H E R I C H I A C O L I D O R N M A I R . K . . J A H N I G , F .

S P E C T R A L P R O P E R T I E S OF 9 - A M I N O A C R I D I N E A N D T H E I R 2 9 4

C H A N G E S I N D U C E D BY E N V I R Ö D E N T A L C O N D I T I O N S I N

B I O L O G I C A L M E M B R A N E S

GRZES1EK. S . , DENCMER, N . A .

WATER P E N E T R A T I O N I N M I C E L L E S B Y F T - I R . . . 2 9 6

S P E C T R O S C O P Y ; A Q U A N T I T A T I V E A P P R O A C H

P R I E T O , M . J . E . , V I L L A L A I N . J . .

F E R N A N D E Z , J . C . G .

T H E L O C A T I O N OF C O E N Z Y M E Q10 I N P H O S P H O L I P I D 2 9 9 B I L A Y E R S A S P R O B E D BY L A N T H A N I D E S H I F T R E A G E N T S O N D A R R Q A . M . . Q U I N N , P . J .

X V


C h a p t e r I V e : N a t u r a l p i g m e n t s 3 0 3

S C H E E R . Η . , 3 0 5 I N V I T E D L E C T U R E

N A T U R A L T E T R A P Y R R O L I C P I G M E N T S S C H E E R , H .

L U T Z t Μ . 3 1 0


P R O B I N G P H O T O S Y N T H E T I C S T R U C T U R E S U S I N G R E S O N A N C E

RAMAN S P E C T R O S C O P Y OF T H E I R P I G M E N T S

L U T Z . Μ . . R O B E R T , Β .

S T Q C K B U R G E R . Μ . 3 1 ?


S T R U C T U R A L A N D K I N E T I C R E S O N A N C E RAMAN S T U D I E S

ON B A C T E R I O R H O D O P S I N ' S R E T I N A L CHROMOPHORE

A L S H U T H , T . , H I L D E B R A N D T , P . ,

S T Q C K B U R G E R . M .

K A I S E R , U l . . 3 2 5


T H E D Y N A M I C S OF T H E F I R S T S T E P S OF P H O T O C Y C L E

OF B A C T E R I O R H O D O P S I N

Z I N T H , W . , N U S S , M . G . , P O L L A N T , H . J . ,

F R A N Z , M . A . , K A I S E R . U.

A V A R M A A . R . A . 3 3 2


H I G H R E S O L U T I O N O P T I C A L S P E C T R O S C O P Y OF

C H L O R O P H Y L L A N T E D N A T U R A L L Y P I G M E N T S A T

LOW T E M P E R A T U R E

A V A R M A A . R . A . . R E B A N E , K .

A R E S O N A N C E RAMAN STUDY OF B A C T E R I A L R E A C T I O N 3 3 8

C E N T E R S : S T R U C T U R E OF T H E P R I M A R Y DONOR

R O B E R T , B . . L U T Z , Μ .

I M I D A Z O L A T E C O M P L E X E S OF F E R R O P R O T O P O R P H Y R I N E 3 4 2

A S M O D E L S FOR H E M O P R O T E I N S

A R E S O N A N C E RAMAN S T U D Y

D E S B O I S . A . . L U T Z , Μ .

x v i

C O M P A R I S O N D E S S P E C T R E S E L E C T R O N I Q U E S E T RAMAN

DE R E S O N A N C E DE P O L Y E N A L S M O D E L E S E T D E P R O D U I T S

DE P H O T O T R A N S F O R M A T I ON DU R E T I N A L TOUT T R A N S

A B O A L Y , M . M . , B A R O N . M . H . , B E L L O C , J . ,

D E L A T O U R , T . , F A V R O T , J .

T R A N S V E R S E L O C A T I O N OF T H E R E T I N A L S C H I F F ' S B A S E

I N B A C T E R I O R H O D O P S I N A N D R H O D O P S I N . S U R F A C E -

E N H A N C E D RAMAN S P E C T R O S C O P Y AND QUANTUM C H E M I C A L

S T U D Y

N A B I E V . I . R . . E F R E M O V , R . G . ,

CHUMANOV , G . D . , A B D U L A E V , N . G .

R E S O N A N C E RAMAN S T U D I E S OF T H E C O N F O R M A T I O N OF

A L L - T R A N S C A R O T E N O I D S I N L I G H T H A R V E S T I N G

S Y S T E M S OF P H O T O S Y N T H E T I C B A C T E R I A

I W A T A , K . , H A Y A S H I , H . , T A S L M I . M .

R E S O N A N C E RAMAN S P E C T R A OF A S T R U C T U R A L S U B U N I T

OF Β 8 7 3 I N T H E R . R U B R U M B A C T E R I O C H L O R O P H Y L L

L I G H T H A R V E S T I N G P R O T E I N

C A L L A H A N . P . M . . C O T T O N , T . M . , L O A C H , P . A .

R O L E D E S M O L E C U L E S P O L Y E N I Q U E S DANS L A . .

P I G M E N T A T I O N D E S CORAUX ET D E S C O Q U I L L A G E S

M E R L I N . J . C . . D E L E - D U B O I S , M . L .

R E S O N A N C E RAMAN S P E C T R A OF P H Y C O B I L I P R O T E I N S A N D P H Y C O B I L I SOMES FROM B L U E - G R E E N A L G A A N A C Y S T I S N I D U L A N S

S Z A L Q N T A I . B . . GOMBOS , Z . , C S I Z M A D I A , V .

R E S O N A N C E RAMAN S T U D I E S OF M E T A L T E T R A K I S ( N -M E T H Y L P Y R I D I N I U M ) P O R P H Y R I N - A S S I G N E M E N T S ; S T R U C T U R E S E N S I T I V E AND S P E C I E S E Q U I L I B R I A L I N E S B L O M , N . , S T R Q M M E N . P . P . . N A K A M O T O , K .

L I G H T - I N D U C E D F O U R I E R T R A N S F O R M I N F R A R E D

S P E C T R O S C O P Y OF T H E P R I M A R Y DONOR O X I D A T I O N I N

B A C T E R I A L P H O T O S Y N T H E S I S

N A B E D R Y K . E . . T A V I T I A N , B . A . , M A N T E L E , W . ,

B R E T O N , J .

χ ν i i

F O U R I E R T R A N S F O R M I N F R A R E D < F T I R ) S P E C T R O S C O P I C 3 7 0 I N V E S T I G A T I O N S I N B A C T E R I A L P H O T O S Y N T H E S I S : I N T E R M E D I A T E A C C E P T O R R E D U C T I O N M A N T E L Ε . U>, , N A B E D R Y K , E . , T A V I T I A N , B . A . , B R E T O N , J .

V I B R A T I O N A L A N A L Y S I S OF C H R O M O P H O R - C O N F I CURAT I ONS 3 7 3

I N B A C T E R I O R H O D O P S I N D U R I N G T H E P H O T O C Y C L E

U S I N G F T - I R D I F F E R E N C E S P E C T R O S C O P Y

G E R U E R T . Κ . . S I E B E R T , F . , P A R D O E N , J . Α . ,

W I N K E L , C , L U G T E N B U R 6 , J .


C h a p t e r I V f : I n t e r a c t i o n s i n b i o l o g i c a l s y s t e m s 3 7 7

H E L E N E , C . 3 7 ? I N V I T E D L E C T U R E

Μ Ε C A N I S H E DE R E C O N N A I S S A N C E D E S S E Q U E N C E S

D ' A C I D E N U C L E I QUE

H E L E N E , C .

B E R T O L U Z Z A . A . 3 8 1

I N V I T E D L E C T U R E RAMAN S P E C T R O S C O P I C S T U D I E S ON T H E M O L E C U L A R I T T E R A C T I O N S OF P H O S P H O L I P I D S B E R T O L U Z Z A . A .

P E Z Q L E T , M . 3 8 7


L I P I D - P R O T E I N I N T E R A C T I O N S I N MODEL M E M B R A N E S

B Y RAMAN S P E C T R O S C O P Y

P E Z Q L E T , M . . C A R R I E R , D . , L A F L E U R , M .

G E R A R D . D . 3 ? 3

I W I T E D L E C T U R E

F L U O R E S C E N C E S P E C T R O S C O P Y : A U S E F U L T O O L T O

S T U D Y T H E C O N F O R M A T I O N ; PY f s f tM ICS A N D

I N T E R A C T I O N S OF P R O T E I N S

G E R A R D . P . . L U X , B . , F O L L E N I U S , Α . ,

K I L H O F F E R , N . C .

x v i i i

A P P L I C A T I O N S OF f V W N S P E C T R O S C O P Y TO O P H T A L M O L O - 3 9 7 G I C A L F I E L D : RAMAN S P E C T R A OF P A T H O L O G I C A L AND N O N - P A T H O L O G I C A L L E N S E S A N D OF T H E R E L A T E D P R O S T H E T I C M A T E R I A L S B E R T O L U Z Z A , Α . , F A G N A N Q . C , G A R C I A - R t t l O S , J . V . , M O N T I , P . , T I N T I , A .

C O N F O R M A T I O N P R O P E R T I E S OF SOME C O L L A G E N MODEL 401 P O L Y P E P T I D E S : T H E I N C O R P O R A T I O N OF L - A Z E T I D I N - 2 -C A R B O X Y L I C A C I D ON T H E S T A B I L I T Y OF T H E T R I P L E - H E L I C A L S T R U C T U R E

B E R T O L U Z Z A , Α . , B O N O R A , S . , F I N I , G . , M Q R E L L I . M . A . . V E R D I N I , A . S .

RAMAN S P E C T R O S C O P Y OF G E N E PRODUCT 3 2 <GP 3 2 ) o f 4 0 4

B A C T E R I O P H A G E T 4

QTTQ t C . DE M U L , F . F . M . , 6 R E V E , J .

A S P E C T R O S C O P I C S T U D Y OF T H E E F F E C T OF P H Y S I C A L 4 0 7

P A R A M E T E R S ON HEMA"! O P O R P H Y R I Ν B I N D I N G T O

M E M B R A N E S A N D C E L L S

E H R E N B E R G . Β . . G R O S S , Ε . , M A L I K , Ζ .

U L T R A V I O L E T R E S O N A N C E R t t i A N S P E C T R O S C O P Y OF A 4 1 0

H I G H L Y S P E C I F I C A C Y L - P A P A I N

T Q N G E . P . J . . W H A R T O N , C . W . , S Z A W E L S K I , R . J . ,

K I L L O U G H , P . J . , H E S T E R , R . E .


C h a p t e r I V g : I n v i v o s t u d i e s 4 1 3

D Q G L I A . S . M . 4 1 5 I N V I T E D L E C T U R E

RAMAN S T U D I E S ON L I V I N G C E L L S

D Q G L I A . S . M . . D E L G U I D I C E , S . , M I L A N I , Μ .

M A N F A I T . M . 4 2 1


I N V I V O S P E C T R O S C O P I C S T U D I E S OF A N T I C A N C E R D R U G -

T A R G E T I N T E R A C T I O N S

M A N F A I T . M . . J E A N N E S S O N , P .

X I X

M E R L I N , J . C . . 4 2 7 I N V I T E D L E C T U R E T H E I N V I V O E X P R E S S I O N OF T H E COLOR OF N A T U R A L P I G M E N T S S T U D I E D BY R E S O N A N C E RAMAN S P E C T R O S C O P Y M E R L I N . J . C .

M A N T S C H . H . H . , 4 „

I N V I T E D L E C T U R E ' * "

I N V I V O F T - I R S T U D I E S OF B A C T E R I A L M E M B R A N E S

M A N T S C H . H . H . . M A R T I N , Α . , M O F F A T , D . J . ,

Y A N G , P .

C O N F O R M A T I O N AND O R I E N T A T I O N OF C O N T R A C T I L E 4 3 ? P R O T E I N S I N I N T A C T M U S C L E F I B E R S BY RAMAN S P E C T R O S C O P Y

P I G E Q N - G Q S S E L I N . H . . P E Z O L E T , M . , C A I L L E , J . P .

E T U D E DES C E L L U L E S P I G M E N T A I R E S DE C R U S T A C E S 4 4 2 CAR I D E A P A R MI C R O S P E C T R O M E T R I E S RAMAN DE

R E S O N A N C E ET D ' A B S O R P T I O N V I S I B L E I N V I V O

N O E L . P . Y . . M E R L I N , J . C . , B A I L L Y , S .

P I G M E N T S A N T H O C Y A N I Q U E S DE V I T I S V I N I F E R A . 4 4 5

( P I N O T N O I R ) ETUDE S T R U C T U R A L E P A R S P E C T R O M E T R I Ε

RAMAN DE R E S O N A N C E

B R Q U I L L A R D . R . . S T A T O U A , Α . , M E R L I N , J . C .

S E L E C T I V E O B S E R V A T I O N OF C H L O R O P H Y L L C I N WHOLE 4 4 ?

C E L L S OF D I A T O M S BY R E S O N A N T RAMAN S P E C T R O S C O P Y

W A G N E R . W . D . . W A I D E L I C H , W.

A P P L I C A T I O N OF R E S O N A N C E RAMAN S P E C T R O S C O P Y T O 4 5 2

S T U D I E S OF I N T A C T E R Y T H R O C Y T E S

S M I T H . W . E . . H O E Y , S . , Mc C Q N N E L , A . A . ,

S O M M E R V I L L E , W.

M I C R O - R A M A N L I N E B R O A D E N I N G I N C A R B O N A T E D 4 5 5

H Y D R O X Y A P A T I T E AND D E N T A L E N A M E L

DE M U L . F . F . M . . B O U T E R , P . ,

H O T T E N H U I S , M . H . H . , O T T O , C , G R E V E , J .

A U T H O R S INDEX 4 5 9

THE DYNAMICS OF THK FIRST STEPS OF THE PHOTOCYCLE OF

BACTERIORHODOPSIN

W. Z i n t h , M.C. Nuss, H.J. P o l l a n d , Μ.A. Franz and

W. K a i s e r1

*

P h y s i k Department der Te c h n i s c h e n U n i v e r s i t ä t M ü n c h e n

D 8000 M ü n c h e n Germany

P h o t o s y n t h e s i s i n h a l o b a c t e r i a i s based on the a b i l i t y o f

the p r o t e i n b a c t e r i o r h o d o p s i n (BR) to a c t as a l i g h t - d r i v e n proton

pump /I/. The primary s t r u c t u r e o f b a c t e r i o r h o d o p s i n i s known: the

p o l y p e p t i d e c h a i n c o n t a i n s 248 amino a c i d s and f o l d s i n t o seven

α-helical segments / 2 / . The a b s o r p t i o n p r o p e r t i e s o f BR a r e

determined by the conformation of the pigment molecule r e t i n a l and

i t s i n t e r a c t i o n s w i t h the p r o t e i n . R e t i n a l i s bound i n BR v i a a

S c h i f f base to one l y s i n e o f the p o l y p e p t i d e c h a i n . I n t h e

l i g h t - a d a p t e d form o f BR, the r e t i n a l molecule has t h e a l l - t r a n s

c o n f i g u r a t i o n and the S c h i f f base i s protonated / 3 / . During the

photochemical c y c l e the a b s o r p t i o n p r o p e r t i e s o f BR change

s u b s t a n t i a l l y . I n t e r m e d i a t e s t a t e s named K, L, M, ... have been

found. During the c o u r s e o f the c y c l e the r e t i n a l adapts the 1 3 - c i s

c o n f i g u r a t i o n and the S c h i f f base l o o s e s i t s p r o t o n . The

photochemical c y c l e i s completed a f t e r ~ 10 ms, when the i n i t i a l

l i g h t - a d a p t e d form o f BR i s reached /2,4/. The f i r s t e v e n t s o f the

p h o t o c y c l e of BR, where the o p t i c a l energy i s s t o r e d i n the

m o l e c u l e s , have been s t u d i e d i n a number o f p u b l i c a t i o n s /5-12/.

U n f o r t u n a t e l y , the e x p e r i m e n t a l r e s u l t s and the i n t e r p r e t a t i o n o f

the f i r s t m o l e c u l a r p r o c e s s e s a r e not unambiguous.

In t h i s L e t t e r we p r e s e n t a summary o f e x t e n s i v e e x p e r i m e n t a l

i n v e s t i g a t i o n s u s i n g time r e s o l v e d p i c o s e c o n d and femtosecond

t e c h n i q u e s . We a p p l i e d advanced e x p e r i m e n t a l t e c h n i q u e s : the time

r e s o l u t i o n was improved down to 50 f s , a h i g h - s e n s i t i v i t y d e t e c t i o n

system gave a c c u r a t e d a t a a t a v e r y low e x c i t a t i o n o f the specimen

(always s m a l l e r than one photon per t e n BR-molecules) and a v a r i e t y

of e x c i t a t i o n and probing f r e q u e n c i e s was a p p l i e d /12,13/.

D i f f e r e n t BR samples were i n v e s t i g a t e d : d e u t e r a t e d BR,

non-deuterated BR, and BR c o n t a i n i n g the s t e r i c a l l y f i x e d

9 - 1 2 - p h e n y l r e t i n a l /14/. The combination o f a l l e x p e r i m e n t a l

r e s u l t s p r o v i d e s a new and c o n s i s t e n t p i c t u r e o f the f i r s t e v e n t s

o f the p h o t o c y c l e o f b a c t e r i o r h o d o p s i n .

M a t e r i a l and Methods

B a c t e r i o r h o d o p s i n ( i n the p u r p l e membrane) was pr e p a r e d from

Halobacterium halobium a c c o r d i n g to t h e procedure g i v e n i n Ref.15.

BR was measured a t pH7 and room temperature. D e u t e r a t e d samples

were prepared ( s e e Ref.13) by r e p e a t e d l y suspending p u r p l e

3 2 5

3 2 6

membranes i n D2O, i l l u m i n a t i n g them s t r o n g l y and c e n t r i f u g a t i n g

them. The exchange of the hydrogen by deuterium a t the S c h i f f b a s e

n i t r o g e n was confirmed by resonance Raman s p e c t r o s c o p y .

The p r i n c i p l e of t h e time r e s o l v e d experiments was as f o l l o w s :

B a c t e r i o r h o d o p s i n was e x c i t e d by a f i r s t u l t r a s h o r t l i g h t p u l s e

which t r i g g e r e d the photochemical r e a c t i o n . A second, p r o p e r l y

d e l a y e d probing p u l s e monitored absorbance changes induced by the

t r a n s i e n t i n t e r m e d i a t e s . V a r y i n g the time d e l a y between e x c i t a t i o n

and probing p u l s e s one was a b l e to s t u d y the dynamics o f the

a b s o r p t i o n changes. The e x p e r i m e n t a l systems a r e d e s c r i b e d i n

d e t a i l i n e a r l i e r p u b l i c a t i o n s /12,13/.

R e s u l t s

Time r e s o l v e d measurements o f l i g h t - i n d u c e d absorbance changes a r e

shown i n F i g . 1 and 2. I n F i g . 1 the absorbance changes from the

v e r y f i r s t e v e n t s a r e p r e s e n t e d . They were measured by u s i n g

u l t r a s h o r t e x c i t i n g and p r o b i n g p u l s e s o f 160 f s ( 1 . 6 · 1 0 ~1 3

s )

d u r a t i o n (λ = 620 nm). T h i s measurement at the h i g h time r e s o l u t i o n

of 50 f s e x h i b i t s i n t e r e s t i n g d e t a i l s a t v e r y e a r l y t i m e s . The d a t a

of F i g . 2 were rec o r d e d u s i n g longer e x c i t i n g and probing p u l s e s o f

4 ps d u r a t i o n . The v e r y f i r s t s t e p s around time z e r o a r e no l o n g e r

seen . But the e v o l u t i o n of the system a t l a t e r times up t o 300 ps

i s c l e a r l y s e e n . The v a r i o u s absorbance changes observed on the

1—1

ρ 1.0

! ι ι 1 1

o L J

< 1 φ cn c

J λ e x c = 6 20 nm —

if λ p r =. 620 nm

5 0

υ c

j* t P = 160 f s _

f -0.5 J 0 ΙΛ j <

-1.0 1 1 1 1

Oeloy T i m e t D CpsecD

F i g . l

T r a n s i e n t absorbance changes i n b a c t e r i o r h o d o p s i n induced

by an e x c i t i n g p u l s e (λ = 620 nm, d u r a t i o n 160 f s ) and

probed a t λ = 620 nm. The v e r y r a p i d k i n e t i c s o f 430 f s

and 5 ps r e f l e c t t h e formation of the i n t e r m e d i a t e s t a t e

J and K.

327

D e l a y T i m e \ D C p s 3

F i g . 2

T r a n s i e n t absorbance changes i n b a c t e r i o r h o d o p s i n

measured w i t h p u l s e s of 4 ps d u r a t i o n . E x c i t i n g p u l s e at

λ = 540 nm and probing p u l s e a t λ = 623 nm. The longer

d u r a t i o n o f the p u l s e s smears out the i n f o r m a t i o n around

time z e r o which can o n l y be measured w i t h s h o r t e r p u l s e s

( s e e F i g . 1 ) .

femtoseond and picosecond time s c a l e (probing wavelengths λ = 620

nm) a r e a s f o l l o w s : ( i ) A s t r o n g peak of induced absorbance o c c u r s

a t time z e r o ( s e e F i g . l ) . We c o u l d show t h a t t h i s apparent

absorbance i n c r e a s e i s not r e l a t e d to a photochemical p r o c e s s ; i t

i s due t o a n o n l i n e a r o p t i c a l p r o c e s s r e s u l t i n g from the hexagonal

arrangement o f the p r o t e i n i n the p u r p l e membrane (second harmonic

g e n e r a t i o n ) /13/. ( i i ) A f t e r the i n i t i a l peak the a b s o r p t i o n

d e c r e a s e s v e r y r a p i d l y due to the formation o f the e x c i t e d

e l e c t r o n i c s t a t e BRS1. ( i i i ) With a time c o n s t a n t of 430+50 f s the

a b s o r p t i o n again i n c r e a s e s ( s e e F i g . l ) . With t h i s time c o n s t a n t the

s t r o n g l y a b s o r b i n g i n t e r m e d i a t e J i s formed. ( i v ) The g e n e r a t i o n

o f the t h i r d i n t e r m e d i a t e Κ w i t h the time c o n s t a n t of 5±2 ps ( s e e

F i g . 2 ) c a u s e s the subsequent s m a l l r e l a t i v e absorbance d e c r e a s e ,

( v ) The absorbance change remains c o n s t a n t f o r the f u r t h e r

o b s e r v a t i o n time o f 300 p s .

P i c o s e c o n d i n v e s t i g a t i o n s a t a l a r g e number of o t h e r probing

f r e q u e n c i e s support the i n t e r p r e t a t i o n given above /12/. A l l d a t a

f i t the model where the t h r e e i n t e r m e d i a t e s t a t e BRS1, J , and Κ a r e

formed one a f t e r t h e o t h e r w i t h the time c o n s t a n t s T B R S ι -Μ -0.43 ps

and TJ-»K=5 p s . The p i c o s e c o n d i n v e s t i g a t i o n s a l l o w to determine the

absorbance s p e c t r a of the i n t e r m e d i a t e s shown i n F i g . 3 . These

s p e c t r a t o g e t h e r w i t h time r e s o l v e d f l u o r e s c e n c e measurements

s t r o n g l y support the i n t e r p r e t a t i o n t h a t ( i ) BRS1 i s an e x c i t e d

e l e c t r o n i c s t a t e , whereas ( i i ) the ( n o n - e m i t t i n g ) s t a t e s J and Κ

ar e e l e c t r o n i c ground s t a t e s .

328

F i g . 3

Absorption s p e c t r a o f b a c t e r i o r h o d o p s i n (BR) and of the

i n t e r m e d i a t e s t a t e s BRS1, J and K. Data a r e deduced from

p i c o s e c o n d e x c i t e / p r o b e experiments a t a v a r i e t y of

probing wavelengths. An e f f i c i e n c y η = 0.6 f o r the

formation o f s t a t e s J and Κ i s assumed.

The_Molecular_Mechanism

Knowing the dynamics of the f i r s t e v e n t s i n n a t i v e BR we want to

d i s c u s s the r e l a t e d m o l e c u l a r p r o c e s s e s : Measurements w i t h

d e u t e r a t e d and non-deuterated BR samples a r e shown i n F i g . 4 ( f o r

wavelengths s e e F i g . l ) . They were recorded by femtosecond l i g h t

p u l s e s . F i g . 4 a and Fig.4b g i v e i d e n t i c a l r e s u l t s i . e . t h e r e i s no

i n d i c a t i o n of a deuterium e f f e c t i n the formation of i n t e r m e d i a t e

J . I n numerous pi c o s e c o n d experiments we have shown t h a t a l s o the

formation of s t a t e Κ does not depend on d e u t e r a t i o n . Our data a r e

i n c o n t r a d i c t i o n to p r e v i o u s p u b l i c a t i o n s , where h i g h e x c i t a t i o n

l e v e l s were used /8,16/. The absence o f a deuterium e f f e c t on the

femtosecond and p i c o s e c o n d dynamics o f b a c t e r i o r h o d o p s i n i s a

s t r o n g i n d i c a t i o n t h a t a t r a n s f e r o f the proton a t the r e t i n a l

S c h i f f base l i n k a g e i s not the primary photochemical p r o c e s s i n BR.

On the o t h e r hand, the s t r o n g s i m i l a r i t y of the a b s o r p t i o n s p e c t r a

o f i n t e r m e d i a t e s J and K, where the r e t i n a l i s i s o m e r i z e d to t h e

1 3 - c i s c o n f i g u r a t i o n , i n d i c a t e t h a t J a l r e a d y c o n t a i n s 1 3 - c i s

r e t i n a l . That i n t e r p r e t a t i o n i s supported by time r e s o l v e d

measurements w i t h BR c o n t a i n i n g the s t e r i c a l l y f i x e d

329

Ο 1 2 3 4 5

1 2 3 4 5

D e l a y T i m e t Q C p s e c D

F i g . 4

T r a n s i e n t absorbance changes measured w i t h femtosecond

l i g h t p u l s e s . E x c i t a t i o n and probing wavelengthes 620 nm.

a) n a t i v e BR ( p u r p l e membranes suspended i n H2O) b) d e u t e r a t e d BR ( p u r p l e membranes suspended i n D2O, where hydrogen a t the S c h i f f base was exchanged by a

d e u t e r i u m ) .

There i s no deuterium e f f e c t i n t h e f i r s t photochemical

s t e p s .

9 - 1 2 - p h e n y l r e t i n a l /14/. Here the e x c i t e d e l e c t r o n i c s t a t e has an

i n c r e a s e d l i f e t i m e o f 10 ps and no photoproducts a r e formed. The

l a c k o f a ground s t a t e photoproduct i n t h e system where

i s o m e r i s a t i o n i s b l o c k e d s t r o n g l y s u p p o r t s the n o t i o n t h a t

i s o m e r i s a t i o n i s t h e f i r s t m o l e c u l a r mechanism o f the p h o t o c y c l e o f

b ac t e r i ο rhodops i η.

3 3 0

S,

l s o m e r i sat ion R e l a x a t i o n

R e a c t i o n Coordinate

F i g . 5

Energy s u r f a c e diagram i l l u s t r a t i n g t h e primary s t e p s o f

the p h o t o c y c l e i n b a c t e r i o r h o d o p s i n w i t h a l l - t r a n s to

1 3 - c i s i s o m e r i s a t i o n o c c u r i n g i n the v e r y f i r s t s t e p

forming s t a t e J w i t h i n 430 f s .

C o n c l u s i o n s

The f i r s t m o l e c u l a r e v e n t s a r e summarized i n the s c h e m a t i c energy

s u r f a c e diagram o f F i g . 5 . The absorbed photon promotes BR to the

e x c i t e d s t a t e s u r f a c e Si . Here a f i r s t rearrangement o f the

molecule l e a d s to the bottom o f the Si s u r f a c e ( s t a t e BRS1). From

here p a r t i t i o n t o the o r i g i n a l ground s t a t e BR and to the

i s o m e r i z e d 1 3 - c i s ground s t a t e J t a k e s p l a c e w i t h i n 430 f s .

Apparently t h e r e i s no energy b a r r i e r a g a i n s t the formation of J . The J to Κ t r a n s i t i o n i s a g r o u n d - s t a t e p r o c e s s where a

rearrangement o f the p r o t e i n s u r r o u n d i n g and r e l a x a t i o n p r o c e s s e s

cause the a b s o r p t i o n changes.

The experiments r e p o r t e d h e r e i n d i c a t e t h a t t h e primary p r o c e s s i n

the p h o t o c y c l e o f b a c t e r i o r h o d o p s i n i s a v e r y r a p i d

p h o t o - i s o m e r i s a t i o n which o c c u r s w i t h i n 430 f s .

Acknowledgement:

The authors acknowledge v a l u a b l e c o n t r i b u t i o n s o f P r o f e s s o r

D . O e s t e r h e l t and coworkers.

3 3 1

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