kinetic studies of retinol addition radicals · 2011-01-07 · kinetic absorption profile for the...

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Kinetic studies of retinol addition radicals

Ali El-Agamey,*a,b,c Shunichi Fukuzumi,*a,d K. Razi Naqvi,e and David J McGarveyb

aDepartment of Material and Life Science, Graduate School of Engineering, Osaka

University, Suita, Osaka 565-0871, Japan; bSchool of Physical and Geographical

Sciences, Keele University, Keele, Staffordshire, ST5 5BG, UK; cChemistry Department,

Faculty of Science, Mansoura University, New Damietta, Damietta, Egypt; dDepartment

of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea; eDepartment

of Physics, Norwegian University of Science and Technology (NTNU), N-7491,

Trondheim, Norway.

*Corresponding authors: Ali El-Agamey (Osaka University); Shunichi

Fukuzumi (Osaka University)

E-mails: [email protected]; [email protected] Tel. No.: +81-

0668797369; Fax No.: +81-0668797370

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011

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Contents

Fig. S1 Transient spectra of 2-PyrS• obtained following 266 nm laser photolysis of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in air-saturated methanol (laser energy ~7 mJ). The inset shows the transient profiles at 380 and 490 nm.

Fig. S2 Transient absorption spectra obtained following LFP (266 nm) of phenyl disulfide (~6 × 10–4 M) in air-saturated methanol (laser energy ~10 mJ). Fig. S3 Normalized kinetic absorption profiles for the decay of PhS• at 450 nm in air- and argon-saturated methanol (laser energy ~4 mJ). Fig. S4 Transient spectra of 2-PyrS-retinol• obtained following 266 nm laser photolysis of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~5.0 × 10–5 M) in air-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 2-PyrS-retinol• at 380 nm. Fig. S5 Transient spectra of PhS-retinol• obtained following 266 nm laser photolysis of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~5.0 × 10–5 M) in air-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of PhS-retinol• at 380 nm. Fig. S6 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~1.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in air-saturated cyclohexane at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 4-PyrS-retinol• at 380 nm. Fig. S7 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in argon-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 4-PyrS-retinol• at 380 nm.


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Fig. S8 Plots of pseudo-first order rate constants (kobs) for formation of PhS-retinol•, 4-PyrS-retinol• or 2-PyrS-retinol• at 380 nm, from the reaction of retinol with phenyl disulfide, 4, 4`-dipyridyl disulfide or 2, 2`-dipyridyl disulfide, respectively in air-saturated methanol versus the concentration of retinol (laser energy ~4.0 mJ). Fig. S9 Kinetic absorption profiles for the formation of 4-PyrS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol in air-saturated methanol. Fig. S10 Kinetic absorption profiles for the formation of 2-PyrS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol in air-saturated methanol. Fig. S11 Kinetic absorption profiles for the formation of PhS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of phenyl disulfide (~6.0 × 10–4 M) in the presence of retinol in air-saturated methanol. Fig. S12 Arrhenius plot for the slow growth (at 380 nm) generated from the reaction of 4-PyrS• (4,4`-dipyridyl disulfide ~2 × 10–4 M) and retinol (~8.0 × 10–5 M), in argon-saturated methanol (laser energy ~4 mJ). Fig. S13 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in air-saturated methanol at 334 K (laser energy ~4 mJ). The inset shows a kinetic absorption profile of 4-PyrS-retinol• at 380 nm. Fig. S14 Eyring plots for the slow growth (at 380 nm) generated from the reaction of 4-PyrS• or 2-PyrS• with retinol (~8.0 × 10–5 M), in argon-saturated methanol (laser energy ~4 mJ). Fig. S15 Transient profiles, at 380 nm, for 4-PyrS-retinol• and 4-PyrS• in argon-saturated methanol at 334 K (laser energy ~4 mJ).


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Fig. S16 Transient profiles, at 380 nm, for 2-PyrS-retinol• and 2-PyrS• in argon-saturated methanol at 334 K (laser energy ~4 mJ). Fig. S17 Transient profile of PhS-retinol•, at 380 nm, following 266 nm laser photolysis (laser energy ~4 mJ) of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~9.0 × 10–5 M), in argon-saturated methanol at 333 K. Fig. S18 Normalized kinetic absorption profiles for the decay of 4-PyrS-retinol• at 380 nm in methanol at various oxygen concentrations (5, 21, 50 and 100%) formed following 266 nm laser photolysis (laser energy ~4 mJ) of 4, 4`-dipyridyl disulfide (~2 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M). The inset shows plots of pseudo-first order rate constants (kobs) for the fast and slow decay of 4-PyrS-retinol•, at 380 nm, versus the oxygen concentration. Fig. S19 The influence of temperature on the normalized transient profiles, at 380 nm, of 2-PyrS-retinol• following 266 nm laser photolysis (laser energy ~4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~8 × 10–5 M), in air-saturated methanol. Fig. S20 Plots of pseudo-first order rate constants (kobs) for the fast and slow decay of PhS-retinol• at 380 nm, generated following 266 nm laser photolysis of phenyl disulfide (~6 × 10–4 M) with retinol (~9.0 × 10–5 M) in methanol, versus the oxygen concentration (laser energy ~4 mJ). The inset shows normalized kinetic absorption profiles for the decay of PhS-retinol•, at 380 nm, at various oxygen concentrations (1, 5, 21, 50, 100% and argon). Fig. S21 The influence of temperature on the normalized transient profiles, at 380 nm, of PhS-retinol• following 266 nm laser photolysis (laser energy ~4 mJ) of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~9.0 × 10–5 M), in air-saturated methanol. Table S1: Values of kobs for the slow absorption rise at 380 nm following 266 nm LFP (laser energy ~4 mJ) of 4, 4`-dipyridyl disulfide (~2 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M), in argon-saturated methanol at different temperatures.


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Table S2: Values of kobs for the slow absorption rise at 380 nm following 266 nm LFP (laser energy ~4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M), in argon-saturated methanol at different temperatures.


6

0

0.01

0.02

0.03

400 440 480 520

0.47 µs3.19 µs8.14 µs16.59 µs87.20 µs

Wavelength/ nm

ΔA

0

0.02

0 25 50 75 100

380 nm490 nmΔ

At/ µs

Fig. S1 Transient spectra of 2-PyrS• obtained following 266 nm laser photolysis of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in air-saturated methanol (laser energy ~7 mJ). The inset shows the transient profiles at 380 and 490 nm.


7

0

0.02

0.04

400 450 500 550

0.52 µs2.58 µs6.92 µs17.7 µs88.0 µs

Wavelength/ nm

ΔA

Fig. S2 Transient absorption spectra obtained following LFP (266 nm) of phenyl disulfide (~6 × 10–4 M) in air-saturated methanol (laser energy ~10 mJ).


8

0

0.005

0.01

0.015

0 25 50 75 100

ArgonAir

ΔA

t/ µs

Fig. S3 Normalized kinetic absorption profiles for the decay of PhS• at 450 nm in air- and argon-saturated methanol (laser energy ~4 mJ).


9

0

0.04

0.08

0.12

0.16

360 405 450 495 540 585 630

0.04 ms0.2 ms0.5 ms1.0 ms

Wavelength/ nm

ΔA 0

0.05

0.1

0 1 2

380 nm

ΔA

t/ ms

Fig. S4 Transient spectra of 2-PyrS-retinol• obtained following 266 nm laser photolysis of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~5.0 × 10–5 M) in air-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 2-PyrS-retinol• at 380 nm.


10

0

0.04

0.08

0.12

0.16

360 405 450 495 540 585 630

0.07 ms0.3 ms1.0 ms1.5 ms

Wavelength/ nm

ΔA 0

0.05

0.1

0 1 2

380 nm

ΔA

t/ ms

Fig. S5 Transient spectra of PhS-retinol• obtained following 266 nm laser photolysis of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~5.0 × 10–5 M) in air-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of PhS-retinol• at 380 nm.


11

0

0.04

0.08

0.12

0.16

360 405 450 495

0.1 ms0.4 ms0.7 ms1.62 ms

Wavelength/ nm

ΔA 0

0.06

0.12

0 1 2

380 nm

ΔA

t/ ms

Fig. S6 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~1.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in air-saturated cyclohexane at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 4-PyrS-retinol• at 380 nm.


12

0

0.04

0.08

0.12

0.16

360 405 450 495 540 585 630

0.02 ms0.12 ms1.5 ms

Wavelength/ nm

ΔA 0

0.04

0.08

0 30 60 90

380 nm

ΔA

t/ ms

Fig. S7 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in argon-saturated methanol at room temperature (laser energy ~4 mJ). The inset shows a kinetic absorption profile for the decay of 4-PyrS-retinol• at 380 nm.


13

0

2

4

6

0 25 50 75

Phenyl disulfide4, 4`-Dipyridyl disulfide2, 2`-Dipyridyl disulfide

k obs/ 1

05 s-1

[retinol]/ µM

Fig. S8 Plots of pseudo-first order rate constants (kobs) for formation of PhS-retinol•, 4-PyrS-retinol• or 2-PyrS-retinol• at 380 nm, from the reaction of retinol with phenyl disulfide, 4, 4`-dipyridyl disulfide or 2, 2`-dipyridyl disulfide, respectively in air-saturated methanol versus the concentration of retinol (laser energy ~4.0 mJ).


14

0

0.05

0 15 30 45

1.3 x 10-5 M

2.6 x 10-5 M

ΔA

t/ µs

Fig. S9 Kinetic absorption profiles for the formation of 4-PyrS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol in air-saturated methanol.


15

0

0.05

0.1

0.15

0 15 30 45

2.7 x 10-5 M

4.5 x 10-5 M

ΔA

t/ µs

Fig. S10 Kinetic absorption profiles for the formation of 2-PyrS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol in air-saturated methanol.


16

0

0.05

0.1

0 30 60 90

4.3 x 10-5 M

6.0 x 10-5 M

8.0 x 10-5 M

ΔA

t/ µs

Fig. S11 Kinetic absorption profiles for the formation of PhS-retinol• at 380 nm at various retinol concentrations formed following 266 nm laser photolysis (laser energy ∼4 mJ) of phenyl disulfide (~6.0 × 10–4 M) in the presence of retinol in air-saturated methanol.


17

7

8

9

10

0.003 0.0032 0.0034

ln(k

β/ s-1

)

K/ T

Fig. S12 Arrhenius plot for the slow growth (at 380 nm) generated from the reaction of 4-PyrS• (4,4`-dipyridyl disulfide ~2 × 10–4 M) and retinol (~8.0 × 10–5 M), in argon-saturated methanol (laser energy ~4 mJ).


18

0

0.04

0.08

0.12

360 405 450

0.33 µs21.0 µs130 µs436 µs

Wavelength/ nm

ΔA 0

0.05

0.1

0 150 300 450

380 nmΔA

t/ µs

Fig. S13 Transient spectra of 4-PyrS-retinol• obtained following 266 nm laser photolysis of 4, 4`-dipyridyl disulfide (~2.0 × 10–4 M) in the presence of retinol (~4.0 × 10–5 M) in air-saturated methanol at 334 K (laser energy ~4 mJ). The inset shows a kinetic absorption profile of 4-PyrS-retinol• at 380 nm.


19

-22

-21

-20

-19

0.003 0.0032 0.0034

4, 4`-dipyridyl disulfide2, 2`-dipyridyl disulfide

ln(k

β hT

-1k b-1

)

K/ T

Fig. S14 Eyring plots for the slow growth (at 380 nm) generated from the reaction of 4-PyrS• or 2-PyrS• with retinol (~8.0 × 10–5 M), in argon-saturated methanol (laser energy ~4 mJ).


20

0

0.04

0.08

0.12

0 0.2 0.4 0.6 0.8 1

retinol and 4, 4`-dipyridyl disulfide 4, 4`-dipyridyl disulfide onlyΔ

A

t/ ms

Fig. S15 Transient profiles, at 380 nm, for 4-PyrS-retinol• and 4-PyrS• in argon-saturated methanol at 334 K (laser energy ~4 mJ).


21

0

0.04

0.08

0.12

0.16

0 0.2 0.4 0.6

retinol and 2, 2`-dipyridyl disulfide2, 2`-dipyridyl disulfide onlyΔ

A

t/ ms

Fig. S16 Transient profiles, at 380 nm, for 2-PyrS-retinol• and 2-PyrS• in argon-saturated methanol at 334 K (laser energy ~4 mJ).


22

0

0.05

0.1

0.15

0 150 300 450

ΔA

t/ µs

Fig. S17 Transient profile of PhS-retinol•, at 380 nm, following 266 nm laser photolysis (laser energy ~4 mJ) of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~9.0 × 10–5 M), in argon-saturated methanol at 333 K.


23

0

0.04

0.08

0.12

0 0.5 1 1.5 2 2.5

5 %21 %50 %100 %

ΔA

t/ ms

0

5

10

15

20

0 0.005 0.01

Fast stepSlow step

k obs/ 1

03 s-1

[O2]/ M

Fig. S18 Normalized kinetic absorption profiles for the decay of 4-PyrS-retinol• at 380 nm in methanol at various oxygen concentrations (5, 21, 50 and 100%) formed following 266 nm laser photolysis (laser energy ~4 mJ) of 4, 4`-dipyridyl disulfide (~2 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M). The inset shows plots of pseudo-first order rate constants (kobs) for the fast and slow decay of 4-PyrS-retinol•, at 380 nm, versus the oxygen concentration.


24

0

0.04

0.08

0.12

0.16

0 3 6 9

297 K323 K333 K

ΔA

t/ ms

Fig. S19 The influence of temperature on the normalized transient profiles, at 380 nm, of 2-PyrS-retinol• following 266 nm laser photolysis (laser energy ~4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~8 × 10–5 M), in air-saturated methanol.


25

0

2

4

6

0 0.005 0.01

Fast stepSlow step

k obs/ 1

03 s-1

[O2]/ M

0

0.08

0.16

0 2.5 5 7.5 10

Argon1 %5 %21 %50 %100 %Δ

At/ ms

Fig. S20 Plots of pseudo-first order rate constants (kobs) for the fast and slow decay of PhS-retinol• at 380 nm, generated following 266 nm laser photolysis of phenyl disulfide (~6 × 10–4 M) with retinol (~9.0 × 10–5 M) in methanol, versus the oxygen concentration (laser energy ~4 mJ). The inset shows normalized kinetic absorption profiles for the decay of PhS-retinol•, at 380 nm, at various oxygen concentrations (1, 5, 21, 50, 100% and argon).


26

0

0.03

0.06

0 2.5 5 7.5 10

301 K334 K

ΔA

t/ ms

Fig. S21 The influence of temperature on the normalized transient profiles, at 380 nm, of PhS-retinol• following 266 nm laser photolysis (laser energy ~4 mJ) of phenyl disulfide (~6 × 10–4 M) in the presence of retinol (~9.0 × 10–5 M), in air-saturated methanol.


27

Table S1: Values of kobs for the slow absorption rise at 380 nm following 266 nm LFP (laser energy ~4 mJ) of 4, 4`-dipyridyl disulfide (~2 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M), in argon-saturated methanol at different temperatures.

T/K kobs for the slow absorption rise/ s-1

334 1.78 × 104 327 1.10 × 104 321 7.45 × 103 311 4.25 × 103 296 1.39 × 103

Table S2: Values of kobs for the slow absorption rise at 380 nm following 266 nm LFP (laser energy ~4 mJ) of 2, 2`-dipyridyl disulfide (~3.0 × 10–4 M) in the presence of retinol (~8.0 × 10–5 M), in argon-saturated methanol at different temperatures.

T/K kobs for the slow absorption rise/ s-1

334 3.29 × 104 327 2.14 × 104 321 1.60 × 104 311 8.55 × 103 296 3.48 × 103


kinetic studies of retinol addition radicals · 2011-01-07 · kinetic absorption profile for the...

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