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2-9䠊GroELMDH䠈Rhodanese 䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ A䠖MDH refolding assay B䠖Rhodanese refolding assay

Spontaneous(䠉)䠖ᇶ㉁䛾⮬Ⓨⓗ䛺෌⏕䜢♧䛧䛶䛔䜛䚹 C䠖60 ศ䛻䛚䛡䜛MDH,Rhodanese 䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ

MDH䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ(䕔)䠈Rhodanese 䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ(䕔) GroEL G192X䛾್䛿䠈60ศ䛻䛚䛡䜛GroEL WT䛾 ᐃ⤖ᯝ䜢100 %䛸䛧䛶⟬ฟ䛧䛯䚹 ྛ䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ䛿3ᅇ ᐃ䛾ᖹᆒ䜢♧䛧䠈3ᅇ ᐃ䛾ᶆ‽ㄗᕪ䜢⟬ฟ䛧䛯䚹

52

2-10䠊G192Xኚ␗య䛾䝣䜯䞁䝕䝹䝽䞊䝹䝇య✚䛸䝅䝱䝨䝻䝙䞁ᶵ⬟䛾㛵ಀ 䛭䜜䛮䜜䛾⤖ᯝ䛿60ศ᫬Ⅼ䛷䛾ᩘ್䜢♧䛧䠈MDHRhodanese 䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾

άᛶ ᐃ䛾⤖ᯝ䛿䠈GroEL WT䛾 ᐃ⤖ᯝ䜢100%䛸䛧䛶⟬ฟ䛧䛯䚹 ATPase assay (GroES㠀Ꮡᅾୗ䠖䖃)䠈ATPase assay (GroESᏑᅾୗ䠖䚽) MDH 䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ(䕔)䠈Rhodanese 䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ ᐃ(䕺)

䛭䜜䛮䜜䛾⤖ᯝ䛿䠈3ᅇ ᐃ䛾ᖹᆒ್䜢䝥䝻䝑䝖䛧䠈䜶䝷䞊䝞䞊䛿ᶆ‽ㄗᕪ䜢♧䛩䚹

2-10

䛻䛚䛡䜛

GroEL G192X

ྛኚ␗య䛾䝣䜯䞁䝕䝹䝽䞊䝹䝇య✚䛸

ATPase

άᛶ䠈

MDH䠈Rhodanese

䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾ά ᛶ   ᐃ 䛾⤖ ᯝ 䛷䛿䠈

GroEL WT

䛸ẚ ㍑ 䛧䛶

GroEL G192X

ྛ ኚ ␗ య 䛿᭦ 䛻ά ᛶ 䛜ప ୗ 䛧䛶䛔䜛䛾䛜䜏䜙䜜䛯䚹䛣䛾⤖ ᯝ 䜢ཷ 䛡䛶䠈

GroEL㻌 G192X

ྛኚ␗య䛾

cis䉄 ring

䛻䛚䛡䜛

Open

≧ែ䛻䛺䛳䛶䛔䜛ᗘྜ䛔䜢䜘䜚ᐃ㔞

ⓗ䛺ᡭἲ䛷ゎᯒ䛩䜛䛯䜑䛻

QCM

䛷䛾 ᐃ䜢⾜䛖䛣䛸䛻䛧䛯䚹

22-3-4䠊GroEL G192X

ኚ␗య䛸

GroES

䛾┦஫స⏝ゎᯒ

㐣ཤ䛾◊✲䛻䛚䛔䛶䠈GroEL G192Wኚ␗య䛿

ATP

㠀Ꮡᅾୗ䛷

GroES

䛸⤖ྜ䛩䜛䛸䛔 䛖䛣䛸䛜᫂䜙䛛䛸䛺䛳䛶䛔䜛䛯䜑䠈QCM(Qurtz Crystal Microbalance assay)䛻䛚䛔䛶䠈ྛ

ኚ␗య䛸

GroES

䛸䛾ぶ࿴ᛶ䜢

ATP

㠀Ꮡᅾୗ䛷䛹䛾䜘䛖䛺ኚ໬䛜䜏䜙䜜䜛䛛䛾ᐇ㦂䜢⾜䛳䛯䚹

53

2-11䠊ATP㠀Ꮡᅾୗ䛻䛚䛡䜛GroEL G192Xኚ␗య䛸GroES䛾┦஫స⏝ ᐃ 䝩䝇䝖ศᏊ䛸䛧䛶ESC750䃛M䝉䞁䝃䞊ୖ䛻ᅛᐃ໬䛧䛶䛔䜛䚹

䝀䝇䝖ศᏊ(ῧຍ䛧䛯GroEL) 20 nM ῧຍ䛧䛶GroEL GroES䛸䛾┦஫స⏝䜢ゎᯒ䛧䛯䚹 GroEL WTATP㠀Ꮡᅾୗ䛷䛿GroES䛸⤖ྜ䛧䛺䛔䛾䛷䠈

ATPᏑᅾୗ(+ATP)䠈㠀Ꮡᅾୗ(䇲ATP)䛻䛚䛡䜛┦஫స⏝ゎᯒ䛾⤖ᯝ䜢䛭䜜䛮䜜♧䛩䚹

54

2-12䠊ATPᏑᅾୗ䠈㠀Ꮡᅾୗ䛻䛚䛡䜛GroEL G192Nኚ␗య䛸GroES䛾┦஫స⏝

ATP㠀Ꮡᅾୗ䛻䛚䛡䜛GroEL WT GroES(䖃) ATP㠀Ꮡᅾୗ䛻䛚䛡䜛GroEL G192NGroES(䖃) ATPᏑᅾୗ䛻䛚䛡䜛GroEL WTGroES(䖃) ATPᏑᅾୗ䛻䛚䛡䜛GroEL G192NGroES(䖃)

-200 -150 -100 -50 0

0 50 100 150 200 250 300

Δ 㻲 㻌 (H z)

Time (s)

55

2-11

䛻♧䛧䛯

QCM

䛾⤖ᯝ䜘䜚䠈GroEL WT䛿

ATP

䛾㠀Ꮡᅾୗ䛷䛿ᇶᯈୖ䛻ᅛᐃ໬

䛧䛯

GroES

䛸䛿⤖ྜ䛧䛺䛔䚹䛧䛛䛧䠈ATP䛾Ꮡᅾୗ䛷䛿ᇶᯈୖ䛻ᅛᐃ໬䛧䛯

GroES

䜈⤖ྜ

䛧䛶䛔䜛䚹䛥䜙䛻䠈ATP 䛾㠀Ꮡᅾୗ䛻䛚䛔䛶

GroEL G192X

ྛኚ␗య䛿

ATP

Ꮡᅾୗ䛾

GroEL WT

䜘䜚䜒䛥䜙䛻

GroES

䛾⤖ྜ䛜⏕䛨䛶䛔䜛䚹GroEL䛾

Gly192

䜢௚䛾䜰䝭䝜㓟ṧᇶ 䛻⨨᥮䛧䛯䛣䛸䛷

GroEL G192W

ATP

㠀Ꮡᅾୗ䛷䛥䛘䜒

cis䉄 ring

ഃ䛻

GroES

䛜⤖ྜ

䛧䛶䛔䛯䚹䛣䜜䜘䜚䠈௚䛾

GroEL G192X

ྛኚ␗య䜒䠈䜰䝢䜹䝹䝗䝯䜲䞁䛜

Open

≧ែ䛻䛺䛳䛶 䛚䜚䠈

cis䉄 ring

ഃ䛻䛿

GroES

䛜⤖ྜ䛩䜛䛣䛸䛷ᇶ㉁䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾䜢௓ຓ䛧䛶䛔䛺䛔 䛣䛸䛜⪃䛘䜙䜜䜛䚹䜎䛯䠈ᅗ

2-12

䛷♧䛧䛯䜘䛖䛻䠈ATP Ꮡᅾୗ䛸㠀Ꮡᅾୗ䛷

GroEL G192N

ኚ␗య䛿ᇶᯈ䛻ᅛᐃ໬䛧䛯

GroES

䜈䛾⤖ྜ䛻㐪䛔䛜䜏䜙䜜䛯䚹䛣䛾⤖ᯝ䛸

GroEL G192X

ኚ␗య㛫䛻䛚䛡䜛䝅䝱䝨䝻䝙䞁άᛶ䛾㐪䛔䛛䜙

trans䉄 ring

ഃ䛷䝅䝱䝨䝻䝙䞁ᶵ⬟䛜ാ䛔䛶䛔 䜛ྍ⬟ᛶ䜒⪃៖䛥䜜䜛䚹䛭䛾䛯䜑䠈

trans䇲 ring

ഃ䛻䛚䛡䜛

GroEL

䛾ᶵ⬟䜢᤼㝖䛧䛯

GroEL

䝅䞁䜾䝹䝸䞁䜾ኚ␗య

SR-1

ኚ␗య䜢⏝䛔䛯ᶵ⬟ゎᯒ䜢⾜䛳䛯䚹䛣䛾

SR-1

䛻䛚䛡䜛

Gly192

ṧᇶ䜢

Val䠈Ile䠈Trp

䛻䛭䜜䛮䜜⨨᥮䛧䛯ኚ␗య䜢స〇䛧䠈䛣䜜䜙䛾ኚ␗య䜢⏝䛔䛯䝅䝱䝨 䝻䝙䞁άᛶ䜢 ᐃ䛩䜛䛣䛸䛷䠈䜘䜚ヲ⣽䛺

GroEL G192X

ኚ␗య䛾䝅䝱䝨䝻䝙䞁ᶵ⬟䜢ゎᯒ䛩 䜛䛣䛸䛻䛧䛯䚹

56

2-13䠊SR-1 G192X ኚ␗య䛾䝅䝱䝨䝻䝙䞁ᶵ⬟ゎᯒ A䠊SR-1 G192X ኚ␗య䛾ATPຍỈศゎάᛶ

GroES㠀Ꮡᅾୗ(䕔)䠈GroESᏑᅾୗ(䕔) B䠊SR-1 G192Xኚ␗య䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ

MDH (䕔)䠈Rhodanese (䕔)

57

GroEL㻌 G192X

ኚ␗య䛿䠈ATP䛾㠀Ꮡᅾୗ䛷

GroES

䛜⤖ྜ䛩䜛䛣䛸䜢♧䛧䛯䚹䝅䝱䝨䝻 䝙䞁άᛶ䛾 ᐃ䛻䛚䛔䛶䠈Gly192ṧᇶ䜢⨨᥮䛧䛯ṧᇶ䛻䜘䛳䛶άᛶ䛻㐪䛔䛜䜏䜙䜜䛯䚹䛣䛾 㐪䛔䛿䠈ᇶ㉁䛜

ATP

㠀Ꮡᅾୗ䛷

GroES

䛜⤖ྜ䛩䜛

cis

䉄ring ഃ䛺䛾䛛䠈䜎䛯䛿

ATP

Ꮡᅾ

ୗ䛷

GroES

䛜⤖ྜ䛩䜛䛸⪃䛘䜙䜜䜛

trans

䉄ring ഃ䛷䝸䝣䜷䞊䝹䝕䜱䞁䜾䛜⿵ຓ䛥䜜䛯⤖ᯝ 䜢཯ᫎ䛧䛶䛔䜛䛸⪃䛘䜙䜜䛯䚹䛭䛣䛷䠈䛹䛱䜙䛾䝸䞁䜾䛷䝸䝣䜷䞊䝹䝕䜱䞁䜾䛾௓ຓ䜢⾜䛖䛛䜢䜘䜚 ヲ⣽䛻ゎᯒ䛩䜛䛯䜑䛻䠈GroEL䛾䝅䞁䜾䝹䝸䞁䜾ኚ␗య(SR-1)䛻䛚䛡䜛

Gly192

ṧᇶ䜢௚䛾 䜰䝭䝜㓟ṧᇶ䛻⨨᥮䛧䛯

SR-1 G192X

ኚ␗య䜢స〇䛧䠈䛭䛾䝅䝱䝨䝻䝙䞁ᶵ⬟䛾ゎᯒ䜢⾜䛳 䛯䚹SR-1 G192Xኚ␗య䛷䛒䜜䜀䠈

cis -ring

ഃ䛾䜏䛷䛾ᶵ⬟䛜⤖ᯝ䛻཯ᫎ䛥䜜䜛䛣䛸䛜ᮇᚅ 䛥䜜䜛䚹ᅗ

2-13A

GroEL WT䠈SR-1 WT䠈SR-1 G192X

ኚ␗య䛾

ATP

ຍỈศゎάᛶ䛾

⤖ᯝ䜢♧䛧䛯䚹䛣䛾⤖ᯝ䛻䛚䛔䛶䠈SR-1 WT䛿

GroEL WT 䛾༙ศ⛬ᗘ䛾άᛶ䜢♧䛧䠈SR-1 G䛾༙ศ⛬ᗘ䛾άᛶ䜢♧䛧䠈SR-192X

ኚ␗య䛿

SR-1 WT

䜘䜚䜒䛥䜙䛻పୗ䛧䛯⤖ᯝ䜢♧䛧䛶䛔䛯䚹䛣䜜䛿䠈2䛴䛾䝸䞁䜾䛜

1

䛴䛻䛺䛳䛯䛣䛸䛷

ATP

䛾ຍỈศゎຠ⋡䛜పୗ䛧䛯䛣䛸䛜⪃䛘䜙䜜䜛䚹䛥䜙䛻䠈GroES Ꮡᅾ

ୗ䛷䛿

GroES

㠀Ꮡᅾୗ䜘䜚䜒䛭䜜䛮䜜άᛶ䛜పୗ䛧䛶䛔䛯䛣䛸䛛䜙

GroES

䛸䛾┦஫స⏝䛜

⪃䛘䜙䜜䛯䚹ᅗ

2-13B

䛷♧䛧䛯

Rhodanese refolding assay

䛾⤖ᯝ䛻䛚䛔䛶䠈SR-1 WT䛿

GroEL WT

䛾༙ศ⛬ᗘ䛾䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ䜢♧䛧䛶䛚䜚䠈SR-1 G192Xኚ␗య䛿⨨᥮

䛧䛯䜰䝭䝜㓟ṧᇶ䛾኱䛝䛥䛻䜘䜚άᛶ䛜పୗ䛧䛶䛔䜛䛾䛜䜏䜙䜜䛯䚹䛭䛾୍᪉䛷䠈MDH 䜢ᇶ㉁

䛸䛧䛯䝸䝣䜷䞊䝹䝕䜱䞁䜾άᛶ䛻䛚䛔䛶䠈SR-1 WT䛿䜋䛸䜣䛹άᛶ䜢♧䛧䛶䛔䛺䛛䛳䛯䚹䝅䞁䜾 䝹䝸䞁䜾ኚ␗య

SR-1

䛿䝸䞁䜾㛫䛾䜰䝻䝇䝔䝸䝑䜽䝅䜾䝘䝹䛜⏕䛨䛺䛔䛯䜑䛻୍ᗘ䛰䛡䝅䝱䝨䝻 䝙䞁䝃䜲䜽䝹䛜䜎䜟䜛䛂䝅䞁䜾䝹䝍䞊䞁䜸䞊䝞䞊≧ែ䛃䛻䛺䜛䛸䛥䜜䛶䛔䜛(89)䚹䛣䛾䛯䜑䠈䝅䞁 䜾䝹䝸䞁䜾ኚ␗య䛿

MDH

䛜䜻䝱䝡䝔䜱ෆ㒊䛻ⴠ䛸䛧㎸䜎䜜䛯ᚋ

GroES

䛜ゎ㞳䛫䛪እ䛻ᨺ ฟ䛥䜜䛪άᛶ䛿ᅇ᚟䛧䛺䛔䚹䛧䛛䛧䠈SR-1 G192V䛸

SR-1 G192I

ኚ␗య䛿

SR-1 WT

䛸ẚ

㍑䛧䠈㧗䛔άᛶ䜢♧䛧䛶䛔䛯䚹

2-14

ཬ䜃⾲

2-2

SR-1 G192I

ATP

Ꮡᅾୗཪ䛿㠀Ꮡᅾୗ䛻䛚䛡䜛

GroES

䛸䛾

┦஫స⏝ゎᯒ䛾⤖ᯝ䜢♧䛧䛯䚹ᅗ

2-14

䛻䛚䛔䛶䠈ATP 㠀Ꮡᅾୗ䜘䜚䜒

ATP

Ꮡᅾୗ䛷䛿⃰

58

ᗘ䛜ୖ䛜䜛䛻䛴䜜䛶䜘䜚

GroES

䛸䜘䜚┦஫స⏝䛧䛶䛔䜛䜘䛖䛻䜏䛘䜛䚹䛧䛛䛧䠈䛣䛾䜾䝷䝣䜘䜚┦

஫స⏝䛻䛚䛡䜛ྛ䜹䜲䝛䝔䜱䝑䜽䝟䝷䝯䞊䝍䞊䜢⟬ฟ䛧䛯䛸䛣䜝

ATP

䛾Ꮡᅾୗ䠈㠀Ꮡᅾୗ䛻㛵 䜟䜙䛪ᩘ್䛻኱䛝䛺㐪䛔䛿䜏䜙䜜䛺䛛䛳䛯䚹䛴䜎䜚䠈ATP 䛾᭷↓䛻㛵䜟䜙䛪

GroES

䛸䛾┦஫

స⏝䛿ኚ໬䛧䛺䛔䛾䜢☜ㄆ䛧䛯䚹⾲

2-2

䛻௨๓

SPR(⾲㠃䝥䝷䝈䝰䞁ඹ㬆)䛻䛚䛔䛶 ᐃ䛧䛯

ATP

Ꮡᅾୗ䛾

GroEL WT

ཪ䛿

ATP

Ꮡᅾୗ䠈㠀Ꮡᅾୗ䛻䛚䛡䜛

GroEL G192W

ኚ␗య䛸

GroES

䛸䛾䜹䜲䝛䝔䜱䝑䜽䝟䝷䝯䞊䝍䞊䜢♧䛧䛯䚹䛣䛾

GroEL

䛾ᩘ್䛸

SR-1 G192I

ኚ␗య䛸 䛾ᩘ್䜢ẚ㍑䛩䜛䛸䠈SR-1 G192Iኚ␗య䛿

GroEL

䜘䜚䜒⤖ྜ㏿ᗘ

k

on䛾ᩘ್䛜ᑠ䛥䛔䛣䛸 䛛䜙

GroES

䛸䛾⤖ྜ䛜㐜䛔䚹䛥䜙䛻䠈SR-1 G192Iኚ␗య䛾ゎ㞳㏿ᗘ

k

off

GroEL WT

䜘 䜚䜒ᑠ䛥䛔䛣䛸䛛䜙

GroES

䛸䛾ゎ㞳䛿㐜䛔䚹䛧䛛䛧䠈GroEL G192W ኚ␗య䜘䜚䛿኱䛝䛔䛣䛸 䛛䜙䠈GroES 䛸䛾 ゎ 㞳 䛜 ᪩ 䛔 䛣䛸 䛜 ☜ ㄆ 䛷 䛝 䛯 䚹 䛣䛾 ⤖ ᯝ 䜘 䜚 䠈

SR-1 G192X

ኚ ␗ య 䛿

GroEL G192X

䜘䜚䜒

GroES

䛜⤖ྜ䛧㞴䛟䠈ゎ㞳䛧᫆䛔ᛶ㉁䜢䜒䛳䛶䛔䜛䛣䛸䛜⪃䛘䜙䜜䜛䚹䛣 䜜䛜๓㏙䛾䝅䝱䝨䝻䝙䞁ᶵ⬟ゎᯒ䛾⤖ᯝ䛻཯ᫎ䛥䜜䛶䛔䜛䛸⪃䛘䜙䜜䜛䚹

59

2-14䠊QCM䛻䜘䜛SR-1 G192IATPᏑᅾୗཪ䛿㠀Ꮡᅾୗ䛷䛾GroES䛸䛾┦஫స⏝

A䠊ATP㠀Ꮡᅾୗ䛻䛚䛡䜛SR-1 G192IGroES䛸䛾┦஫స⏝ゎᯒ B䠊ATPᏑᅾୗ䛻䛚䛡䜛SR-1 G192IGroES䛸䛾┦஫స⏝ゎᯒ

A䠈B䛻䛚䛔䛶䠈5 nM(䖃)䠈10 nM(䖃)䠈15 nM(䖃)䠈20 nM(䖃)䠈25 nM(䖃)䜢♧䛧䛶䛔䜛䚹

2-2䠊ᅗ2-14䜘䜚⟬ฟ䛧䛯GroESSR-1 G192I䛾䜹䜲䝛䝔䜱䝑䜽䝟䝷䝯䞊䝍䞊 Kd(M)䠖ゎ㞳ᐃᩘ䠈kon (M-1䞉S-1)䠖⤖ྜ㏿ᗘ䠈koff(S-1)䠖ゎ㞳㏿ᗘ

*Biacore2000䜢౑⏝䛧䛯SPR䝇䝨䜽䝖䝹 ᐃ⤖ᯝ(19)䚹

Sample k

on

(M

-1䞉S-1

) k

off

(S

-1

) K d (M) SR-1 G192I (䇶ATP) 1.39㽢10䈭 1.71㽢10

-3

1.22㽢10

-7

SR-1 G192I (+ATP) 1.37㽢10䈭 1.65㽢10

-3

1.20㽢10

-7

*GroEL WT (+ATP) 1.76㽢10䈯 1.03㽢10

-2

6.08㽢10

-9

*GroEL G192W(䇶ATP) 3.88㽢10䈯 2.96㽢10

-4

7.63㽢10

-11

*GroEL G192W(+ATP) 6.82㽢10䈯 5.08㽢10

-5

7.30㽢10

-12

60