Molecular Switches

F V F V

	O
S	NHC (CH2)2	N
		O

							NO2			O2
							Cyt. c
S						N	Fe(III)			COx
				e–				e–		H2O
				λ > 475 nm						360 nm < λ < 380 nm

O

+ SNHC (CH2)2 N

OH

O2N

S N

+	Cyt. c
+
+	Fe(III)		COx
+

e–

0 M
P M
	P M

F V F V

F V

F V

F V F V

0 M P M

				e−
	N		N		CH3
S		S		Fe	NH(CH3)2
	O		O		+
					(29)

		NO2		Apo-GOx					NO2
S	(30a)						S	(30a)
S	O		NH				S	O		NH
	(CH2)5							(CH2)5

CH3

+ NH(CH3)2

Fe +

Glucose

Gluconic acid

λ	360nm<λ<380nm
>475nm

e−

+

S N

electrostatic repulsion

	HO
	NO2
	(30b)
S
S	O NH
	(CH2)5

CH3

Fe	NH(CH3)2
	+

CH3

+ NH(CH3)2

Fe +

Glucose

Gluconic acid

M

	40
			30
		A	20
	30	I /	10					(a)
			0
A	20		MRH	MRH SP	MRH SP	SP MRH SP	MRH
			+	+	+	+	+
/			Isomeric State					(b)
I	10
	0
		0				0.2	0.4	0.6

E / V

0 M

M

M

M

M

M

M

M

M

M M

M

M

			R+ / R					R+ / R
A)					I
I
			V					V

B)

Zim

Zim

Zre

C)

∆f

D)
lightintensity	light intensity

θ (degrees)

M

Zre

t (time)

∆θ shift

θ (degrees)

M

M M

M

M 0 0 0 M

M M

M

M

M

M

M M

M

M

F

V

M M

M M

M

M

0 M

0 M

M