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Transcript of A n° }< - SPring-8bioxtal.spring8.or.jp/ja/SPRUC/SSB_6_3.pdf · Mn 4CaO 5ó ùû ÛÊé ì ÔØ...

BL BL38B1

2016.8.29 ( )

II(PSII)

e-

H+

H2O

(NADPH)

(ATP)

II Photosystem II PSII)

•! •!

O2O2

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1.9Mn4CaO5

Umena, Kawakami, Shen, Kamiya, Nature , 2011

PSII

Mn

Mn

Mn

Mn

Mn

B. Kok, et al, (1970), V. K. Yachandra, et al., (1993) H.Dau, et al., (2007)

Kok cycle model Mn4CaO5-cluster

S1

S0 S2

S4 S3S3

e-

O2

e-

e-

e-

H+

H+

H+

H2O

H2OH+

4Mn ( III3, IV)?

4Mn (III2, IV2)

4Mn (IV4)?

4Mn (III, IV3)

2H20 ! 4H+ + 4 e + O2

Mn

Mn

Mn

III? or IV?

III? or IV?

III? or IV?

III? or IV?

(III, IV3)

5-cluster

MnIII? or IV?III? or IV?MnIII? or IV?MnMnIII? or IV?Mn

Mn Mn

X-ray

Mn metals

"! 4 Mn

X-ray

Fluorescence X-ray

Mn4CaO5-

X-ray absorption spectrum from mixed valence Mn metal complex

"!

•! 55% !

•! Crikshank DPI

0.16 (1.9 , 3WU2)

X

1.887 1.89 1.893 1.896 1.899

norm

aliz

ed F/

Io

wavelength (/ )

Mn (IV)O2

Mn(III) 2O3

Mn (II) O

X

Mn (III)

Mn (II)

Mn (IV)

0

10

20

30

40

50

60

Mn1 Mn2 Mn3 Mn4 Ca

0.900A 1.892A 1.896A

Mn (1.892

Mn Ca

0.900 1.892

PSII X

PSII

•! X X •! •!

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Number of Diffraction image

K-

•! X Mn •! •! Mn X

NSL-193L 193.4nm

Beam size: FWHM 4um Pulse power: 1µ J/pls Pulse width: <1.3ns

1

43

25

:50 µm

PSII

Kitano H. et al., Jpn. J. Appl. Phys. (2005)

•!

!!

!! /

•!

!! (dose)

!!

No Process Cylinder shaperesolution ( ) 50-2.5 (2.54-2.50) mosaic range (°) 0.39-0.43 0.34-0.41 No of reflection 1,075,057 1,100,974 R-merge 0.14 (0.85) 0.09 (0.48) <I>/<! (I)> 15.5 (1.5) 25.2 (2.5) completeness (%) 97.0 (90.3) 98.6 (98.3)

0 0.05 0.1

0.15 0.2

0.25 0.3

0 100 200 300 400 500

R-m

erge

Frame number

0 2 4 6 8

10 12

0 100 200 300 400 500

Scal

e fa

ctor

Frame Number

8 10 10

0.05 0.1 0.1

Advantage of cylinder shaped crystal 1

0

0.05

0.1

0.15

0.2

0.25

0.3

0 30 60 90 120 150

Rm

erge

oscilation range (/degree)

cylinder

none

150 °(30° x 5 crystals)

Advantage of cylinder shaped crystal 2 #!Multi-crystal data collection

#!Accurate X-ray Dose estimation

-0.005

0

0.005

0.01

0.015

0.02

0.025

0.03

6530 6535 6540 6545 6550 6555 6560 6565 6570

0deg_none 45deg_none 90deg_none

-0.005

0

0.005

0.01

0.015

0.02

0.025

0.03

6530 6535 6540 6545 6550 6555 6560 6565 6570

0deg_clynd 45deg_cylnd 90deg_cylnd

045

90

045

90

Advantage of cylinder shaped crystal 3

XAFS spectra at different crystal orientations

* (8 ) * 10cm 2cm

NIR (850nm)

NIR

NIR

•! ! etc

•! !! !!

•! XAFS ! X