୧཮ᛶ࢖࢜ࣥࣈࣟࢵࢡඹ㔜ྜయ⃰ཌ⁐ᾮࡢࣛ࢖࢜ࢺࣟࣆࢵࢡ⛛ᗎᵓ㐀ᷓᇉຬḟࠊ 㧗ᶫᑗஓࠊΎỈ ⲁ኱ศ኱Ꮫ
1. ࡣࡌࡵ࡟
⣽⬊ෆ࡟࠾࠸࡚ࢱࣥࣃࢡ㉁ࡸ᰾㓟ࡢᾮѸᾮ┦ศ㞳࡟nOࡼࡾᙧᡂࡉࢀࡿືⓗ࡞㧗ศᏊ㞟ྜయࡣࠊ⣽⬊ෆศ⏬໬ࠊmOOO≀㉁㍺㏦ࠊࢩࢢࢼࣝఏ㐩࡜࠸ࡗࡓከᵝ࡞⏕యࢩࢫࢸ࣒

NN࡟࠾ࡅࡿ㔜せ࡞㠀⭷࢜ࣝ࢞ࢿࣛ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸OࡿࠋࡑࡢࡓࡵࠊᾮѸᾮ┦ศ㞳࡟ࡼࡾᙧᡂࡉࢀࡿ࢜ࣝ࢞

PCBOO SO Oࢿࣛࡢᵓ㐀ࡸືែࡢศᏊㄽⓗ⌮ゎࡀᛴ㏿࡟㐍ࡳࡘࡘ

PSB࠶ࡾࠊ┦ศ㞳⌧㇟ࡢไᚚ࡟ࡼࡿ᪂ࡓ࡞ศᏊࢩࢫࢸ࣒࡬

ᅗ 1PCB-b-PSB ࡢ໬Ꮫᵓ㐀࡜Ỉ⁐ᾮࡀᙧᡂࡍࡿ࣓ࢯᵓ

ࡢᮇᚅࡀ㧗ࡲࡗ࡚࠸ࡿ[1]ࠋ୍᪉ࠊỈ⁐ᛶ㧗ศᏊࡀỈ⁐㐀ࡢᶍᘧᅗᾮ ୰ ࡛ ┦ ศ 㞳 ࡍ ࡿ ⌧ ㇟ ࡣ Aqueous Two-Phase
System (ATPSࠊỈᛶ஧┦⣔)࡜ࡋ࡚▱ࡽࢀ࡚࠾ࡾࠊࢱ

2. ᐇ㦂

ࣥࣃࢡ㉁ࡢ㑅ᢥⓗ࡞ศ㓄࡟ࡼࡿ⢭〇ࡸ⃰⦰࡟฼⏝ࡉ

2-1 ヨᩱ

ࢀ࡚ࡁࡓ[2,3]ࠋ㏆ᖺࠊỈ⁐ᾮࡀ┦ศ㞳ࡍࡿぶỈᛶ㧗ศᏊྍ㏫ⓗ௜ຍ㛤⿣㐃㙐⛣ື㸦RAFT㸧㔜ྜ࡟ࡼࡾࠊ࡛ᵓᡂࡉࢀࡿ୧ぶỈᛶࣈࣟࢵࢡඹ㔜ྜయࡀỈ⁐ᾮ୰

PCB ࣐ࢡࣟ㐃㙐⛣ື๣ࢆྜᡂࡋࠊPSB ࢆ㙐ᘏ㛗ࡍࡿ࡛จ㞟ࡋ࡚ᙧᡂࡍࡿศᏊ㞟ྜయࡀᥦ᱌ࡉࢀ࡚࠾ࡾࠊ୧

ࡇ࡜࡛ PCB-b-PSB ࢆྜᡂࡋࡓ[7]ࠋ㔜ྜ⏕ᡂ≀ࢆศูぶ፹ᛶ㧗ศᏊࡀ␯Ỉᛶ┦஫స⏝࡟ࡼࡾỈᅪ࡛ᙧᡂࡍỿẊࡍࡿࡇ࡜࡛ࠊศᏊ㔞ศᕸࡀ⊃࠸ศᏊ㔞ไᚚࡉࢀࡓ

ࡿศᏊ㞟ྜయ࡜ࡣ␗㉁࡞≀㉁㏱㐣ᛶࡢ㧗࠸᪂ࡓ࡞ศ

ࣈࣟࢵࢡඹ㔜ྜయ⩌ࢆྜᡂࡋࡓࠋGPCᏊ㞟✚య࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ[4,5]ࠋ

࣒ࣛ 㸸TSKgel G5000PWXLࠊTSKgel G3000PWXLࠊᡃࠎࡣࠊ⏕య㐺ྜᛶ࡟ඃࢀࡿ཮ᛶ࢖࢜ࣥ㧗ศᏊ࡛ᵓᐃ㸦ศ㞳࢝⁐㞳ᾮ㸸200 mM NaCl Ỉ⁐ᾮ㸧࡜ 1H-NMRᐃ㸦㔜ᡂࡉࢀࡓࣈࣟࢵࢡඹ㔜ྜయࡀࠊ཮ᛶ࢖࢜ࣥᵓ㐀ࡢ㠀ᑐ⁐፹㸸200 mM NaCl D2O ⁐ᾮ㸧࡟ࡼࡾࣈࣟࢵࢡඹ㔜⛠ᛶ࡟㉳ᅉࡍࡿ཮ᛶ࢖࢜ࣥࡢỈ࿴≧ែࡸ┦஫స⏝ࡢྜయࡢศᏊᵓ㐀ࢆ☜ㄆࡋࡓࠋPCB ࣐ࢡࣟ㐃㙐⛣ື๣┦㐪࡟ࡼࡾ┦ศ㞳ࡋࠊ཮ᛶ࢖࢜ࣥ㧗ศᏊࡢࡳ࡛ᵓ⠏ࡉ࡜ PCB-b-PSB ࡢᩘᖹᆒศᏊ㔞࡜ศᏊ㔞ศᕸࡣࡑࢀࡒ

ࢀࡿ᪂ࡓ࡞ศᏊ⤌⧊యࢆ๰ᡂ࡛ࡁࡿ࡜╔᝿ࡋࡓࠋᮏ◊ࢀ Mn,PCB = 9500ࠊ Mw/Mn,PCB = 1.11ࠊMn,PCB-b-PSB =✲࡛ࡣࠊ཮ᛶ࢖࢜ࣥ㧗ศᏊ࡛࠶ࡿ࣏ࣜ[3-(N-2-࣓ࢱࢡ55800ࠊ Mw/Mn, PCB-b-PSB = 1.08 ࡛࠶ࡾࠊPCB 㙐ࡢ㔜ࣜࣟ࢖ࣝ࢜࢟ࢩ࢚ࢳࣝ-NࠊN-ࢪ࣓ࢳࣝ㸧࢔ࣥࣔࢿ࣮ࢺ

ྜᗘ࡜ PSB 㙐ࡢ㔜ྜᗘࡣࡑࢀࡒࢀ 43ࠊ
158 ࡛࠶ࡗࡓࠋ࢔ࢭࢸ࣮ࢺ]㸦PCB㸧࡜࣏ࣜ[3-(N-2-࣓ࢱࢡࣜࣟ࢖ࣝ࢜௨㝆ࠊࡇࡢࣈࣟࢵࢡඹ㔜ྜయࢆ PCB43-b-PSB158 ࡜⾲࢟ࢩ࢚ࢳࣝ-NࠊN-ࢪ࣓ࢳࣝ㸧࢔ࣥࣔࢿ࣮ࢺࣈࢱࣥࢫࣝグࡍࡿࠋ࣍ࢿ࣮ࢺ]㸦PSB㸧࡛ᵓᡂࡉࢀࡿࣈࣟࢵࢡඹ㔜ྜయ
㸦PCB-b-PSB㸧Ỉ⁐ᾮࡢ࣓ࢯࢫࢣ࣮ࣝ⛛ᗎᵓ㐀ࢆᑠ

2-2 ᐇ㦂᪉ἲゅ X ⥺ᩓ஘㸦SAXS㸧 ᐃ࡟ࡼࡾゎᯒࡋࠊ୧ぶỈᛶࣈSAXS

ᐃࡣࠊ஑ᕞࢩࣥࢡࣟࢺࣟࣥග◊✲ࢭࣥࢱ࣮ࣟࢵࢡඹ㔜ྜయࡢ┦ศ㞳࡟ࡼࡾᙧᡂࡉࢀࡿ⛛ᗎᵓ㐀

BL11 ࡟࡚ࠊ
㹖⥺࢚ࢿࣝࢠ࣮ 8000 eVࠊ࣓࢝ࣛ㛗 1618

࡜ࡑࡢᵓ㐀㌿⛣ࡢⓎ⌧ᶵᵓࢆ᥈ồࡋࡓ㸦ᅗ 1㸧[6]ࠋ

mm ࡜ࡋࠊ᳨ฟჾ࡟ PILATUS 300K (Dectris Co.,Ltd.)ࢆ⏝࠸࡚ ᐃࡋࡓࠋ2 ḟඖᩓ஘ᙉᗘࢹ࣮ࢱࡼࡾࠊ
ゎᯒࢯࣇࢺFit2Dࢆ⏝࠸࡚෇⎔ᖹᆒࡋࡓ1ḟඖᩓ஘ᙉ ᗘࣉࣟࣇ࢓࢖ࣝࢆᚓࡓࠋ⁐ゎᛶヨ㦂ࡣࠊ㐣㓟໬Ỉ⣲ฎ(A)⌮ࡋ࡚ࢪࢳ࢜࣋ࣥࢰ࢚࣮ࢺᮎ➃ࢆ㝖ཤࡍࡿࡇ࡜࡛↓Ⰽ໬ࡋࡓ PCB㸦㔜ྜᗘ㸸34㸧࡜ࢪࢳ࢜࣋ࣥࢰ࢚࣮ࢺᮎ➃࡟ࡼࡾῐ㉥Ⰽ࡟╔Ⰽࡋࡓ PSB㸦㔜ྜᗘ㸸145㸧ࡢq*(a)͵q*ࣈࣞࣥࢻ⁐ᾮࡢΰྜ≧ែࢆ┠どほᐹࡋࠊࡑࢀࡒࢀࡢᒙࡢయ✚ࢆ࣓ࢽࢫ࢝ࢫ఩⨨࠿ࡽィ ࡋࡓࠋ

͹q*q*3㸬⤖ᯝཬࡧ⪃ᐹ(b)
2q* ͹q*q*(c)PCB43-b-PSB158Ỉ⁐ᾮࡢ୍ḟඖSAXSᙉᗘࣉࣟࣇ

3q*࢓࢖ࣝࢆᅗ2(A)࡟♧ࡍࠋ60wt%Ỉ⁐ᾮࡣᩓₔ࡞ᩓ஘q*ࣆ࣮ࢡࢆ♧ࡋ࡚࠾ࡾࠊPCB㙐࡜PSB㙐ࡣ┦ศ㞳ࡋ࡚࠸

(d)
2q*

ࡿࡶࡢࡢ⛛ᗎᛶࡢ㧗࠸࿘ᮇᵓ㐀ࢆᙧᡂࡋ࡞࠿ࡗࡓࠋ50

3q*wt%Ỉ⁐ᾮࡣᵓ㐀ᅉᏊ࡟㉳ᅉࡍࡿ」ᩘࡢ㧗ḟࣆ࣮ࢡ(e)ࢆ♧ࡋࠊ୍ḟࣆ࣮ࢡ㸦q*㸧࡟ᑐࡍࡿ㧗ḟࣆ࣮ࢡࡢᩓ஘࣋ࢡࢺࣝ࡜ࠊࣈࣟࢵࢡඹ㔜ྜయࡢయ✚ศ⋡ࡼࡾࠊPCB(f)┦ࡀࢻ࣓࢖ࣥ࡜࡞ࡗࡓ࣊࢟ࢧࢦࢼࣝࢩࣜࣥࢲ࣮ᵓ㐀ࡢᙧᡂࡀㄆࡵࡽࢀࡓࠋ40 wt%Ỉ⁐ᾮ࡛ࡣᩓ஘ࣆ࣮ࢡࡀඛ㗦໬ࡋ࡚࠾ࡾࠊ᱁Ꮚᵓ㐀ࡢ஘ࢀࡀ኱ᖜ࡟పῶࡋࡓࠋ

(B)

30 wt%Ỉ⁐ᾮࡣᵓ㐀ᅉᏊ࡟㉳ᅉࡍࡿᩓ஘ࣆ࣮ࢡ఩⨨

(b)

(c)

ࡼࡾࠊ࣓ࣛࣛ≧⛛ᗎᵓ㐀࡬ࡢᵓ㐀㌿⛣ࡀㄆࡵࡽࢀࡓ㸦2PCBPSBḟࣆ࣮ࢡࡣᾘ⁛๎࡟ࡼࡾᾘኻ㸧ࠋ20 wt%Ỉ⁐ᾮ࡛ࡣaᩓ஘ࣆ࣮ࢡࡀᗈᖜ໬ࡋ࡚࠾ࡾ᱁Ꮚᵓ㐀ࡢ஘ࢀࡀ㢧ᅾRc

໬ࡋࠊ10 wt%Ỉ⁐ᾮ࡛ࡣᩓ஘ࣆ࣮ࢡࡀᾘኻࡋ࡚࠾ࡾ↓⛛ᗎ໬ࡋࡓࠋࣃࣛࢡࣜࢫࢱࣝ⌮ㄽ࡟ᇶ࡙ࡃᩓ஘㛵ᩘ(d)(e)

࡛ᩓ஘ᙉᗘࣉࣟࣇ࢓࢖ࣝࢆࣇ࢕ࢵࢸ࢕ࣥࢢࡋࡓ⤖ᯝࠊ

L1㧗ศᏊ⃰ᗘࡢపୗ࡜ඹ࡟PCB㙐ࡢయ✚ศ⋡ࡀቑ኱ࡋࠊ

LPCBࢩࣜࣥࢲ࣮ࢻ࣓࢖ࣥࡢභ᪉᭱ᐦ඘ሸᵓ㐀࠿ࡽࢩࣜࣥࢲ࣮ᚄࡢቑ኱ࢆ⤒࡚࣓ࣛࣛᵓ㐀࡬ࡢ⛛ᗎᵓ㐀㌿⛣ࡋࡓࠋᅗ2(B)࡟ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ⟬ฟࡉࢀࡓᅗ 2 (A) PCB43-b-PSB158 Ỉ⁐ᾮࡢ෇⎔ᖹᆒ SAXS ୍ḟ⌮᝿᱁Ꮚࡢᶍᘧᅗࢆ♧ࡋ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ

ඖࣉࣟࣇ࢓࢖ࣝ(B) ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾィ⟬ࡋࡓ

PCB43-b-PSB158ࡢ⃰ཌỈ⁐ᾮࡣỈ࿴ࡋࡓPCB㙐࡜Ỉ⌮᝿᱁Ꮚᵓ㐀ࡢᶍᘧᅗ [Ỉ⁐ᾮ⃰ᗘ㸸(a) 60 wt%ࠊ (b) 50

࿴ࡋࡓPSB㙐ࡀ┦ศ㞳ࡋ࡚࠾ࡾࠊ≉ᐃࡢ⃰ᗘ⠊ᅖ࡟࠾

wt%ࠊ (c) 40 wt%ࠊ (d) 30 wt%ࠊ (e) 20 wt%ࠊ (f) 10࠸࡚㧗ᗘ࡟⛛ᗎ໬ࡋࡓ࣓ࢯᵓ㐀ࢆᙧᡂࡋࠊ⃰ᗘ࡟ᛂࡌwt%] Reproduced with permission from Wily-VCH

࡚ࣔࣝࣇ࢛ࣟࢪ࣮ࡀኚ໬ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

GmbH㧗ศᏊ⃰ᗘ࡟ᛂࡌࡓ⛛ᗎᵓ㐀㌿⛣ᶵᵓࢆ࣏࣐࣮࣍ࣔࣜࣈࣞࣥࢻỈ⁐ᾮࡢ⁐ゎᛶヨ㦂᳨࡛ドࡋࡓ㸦ᅗ 3㸧ࠋ

SAXS↓ⰍPCB࣏࣐࣮࣍ࣔࣜ࡜ῐ㉥ⰍPSB࣏࣐࣮࣍ࣔࣜࡣ⋡࡜୍⮴ࡋࡓࠋࡍ࡞ࢃࡕࠊᾐ㏱ᅽࡢせㄳ࡟ࡼࡿ PCB᫂☜࡟┦ศ㞳ࡋ࡚࠾ࡾࠊỈ⁐ᾮ⃰ᗘ࡟ࡼࡽࡎ PSB ࢤ┦࡬ࡢỈࡢ㑅ᢥⓗ࡞ศ㓄࡟ࡼࡿయ✚ศ⋡࡜⏺㠃᭤⋡ࣝ≧⭾₶┦ࡢయ✚ࡣ୍ᐃ࡛ࠊỈࡀ㑅ᢥⓗ࡟ PCB ┦࡟ࡢኚ໬ࡀ⛛ᗎᵓ㐀㌿⛣ࡢⓎ⌧ᶵᵓ࡛࠶ࡿࡇ࡜ࡀ♧ࡉศ㓄ࡉࢀࡓࠋࡲࡓࠊ┦ศ㞳ࡋࡓ⁐ᾮࡢయ✚ศ⋡ࡣࢀࡓࠋPSB 㙐ࡣࢫࣝ࣍࣋ࢱ࢖ࣥᇶࡢࢫࣝ࣍ࣥ㓟࢔ࢽ࢜ ᐃ࡛ồࡵࡓ⛛ᗎᵓ㐀࠿ࡽィ⟬ࡉࢀࡿయ✚ศࣥ࡜ᅄ⣭࢔ࣥࣔࢽ࣒࢘࢝ࢳ࢜ࣥࡢ㟁Ⲵᐦᗘࡀᑐ⛠ⓗཧ⪃ᩥ⊩࡛࠶ࡿࡓࡵ㟼㟁┦஫స⏝࡟ࡼࡾ఍ྜࡋࡸࡍ࠸ࠋࡇࡢࡓ

[1] S. F. Banani, H. O. Lee, A. A. Hyman, M. K.

ࡵࠊPSB 㙐ࡀࢫࣝ࣍࣋ࢱ࢖ࣥࡢ఍ྜ࡟ࡼࡾࢿࢵࢺ࣮࣡

Rosen, “Biomolecular Condensates: Organizers ofࢡᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜࡛⁐ゎᛶࡀไ㝈ࡉࢀࠊᾐ㏱ᅽ࡟

Cellular Biochemistry”, Nat. Rev. Mol. Cell Biol., 18㸪ࡼࡿ㑅ᢥⓗ࡞Ỉࡢศ㓄ࡀಁࡉࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ

285 (2017).
[2] C. R. Mace, O. Akbulut, A. A. Kumar, N. D.
Shapiro, R. Derda, M. R. Patton, G. M. Whitesides,“Aqueous Multiphase Systems of Polymers andSurfactants

ProvideSelf-Assembling

Step-Gradients in Density”, J. Am. Chem. Soc., 134,9094 (2012).

(a)

(b)

[3] H. Zhao, V. Ibrahimova, E. Garanger, S.

(c)Lecommandoux, “Dynamic Spatial Formation andᅗ㸱 ↓ⰍPCB࣏࣐࣮࣍ࣔࣜ࡜ῐ㉥ⰍPSB࣏࣍ࣔࣜDistribution of Intrinsically Disordered Protein࣐࣮ࡢ㸰ᡂศࣈࣞࣥࢻỈ⁐ᾮࡢእほ [Ỉ⁐ᾮ⃰ᗘ㸸(a) 50

Droplets in Macromolecularly Crowded Protocells”

wt%ࠊ (b) 40 wt%ࠊ (c) 30 wt%] Reproduced withAngew. Chem. 132, 11121 (2020).

permission from Wily-VCH GmbH

[4] A. Blanazs, N. J. Warren, A. L. Lewis, S. P.
Armes, A. J. Ryan, “Self-assembly of Double

4. ࡲ࡜ࡵ

Hydrophilic Block Copolymers in Concentrated␗✀཮ᛶ࢖࢜ࣥ㧗ศᏊ࡛ᵓᡂࡉࢀࡿ୧ぶỈᛶࣈAqueous Solution”, Soft Matter, 7, 6399 (2011).

ࣟࢵࢡඹ㔜ྜయࡀỈ⁐ᾮ≧ែ࡛ࢼࣀࢫࢣ࣮ࣝࡢ⛛ᗎ

[5] S. M. Brosnan, H. Schlaad, M. Antonietti,ᵓ㐀ࢆᙧᡂࡋࠊ㧗ศᏊ⃰ᗘ࡟ᛂࡌ࡚ᵓᡂ཮ᛶ࢖࢜ࣥ㧗“Aqueous Self-Assembly of Purely HydrophilicศᏊจ㞟┦ࡢᾐ㏱ᅽ࡟㉳ᅉࡋ࡚⛛ᗎᵓ㐀㌿⛣ࢆ♧ࡍBlock Copolymers into Giant Vesicles”, Angew.

⌧㇟ࢆぢฟࡋࡓࠋ⏕య㐺ྜᛶ㧗ศᏊ࡛ᵓᡂࡉࢀࡿࢼࣀ

Chem. Int. Ed., 54, 9715 (2015).

ࢫࢣ࣮ࣝࡢỈᛶ஧┦⣔ᵓ㐀య࡛࠶ࡾࠊ⎔ቃ࡟ᛂࡌ࡚ศ

[6] M. Takahashi, A. Shimizu, S. Yusa, Y. Higaki,Ꮚศ⏬࡜ゎᨺࢆไᚚ࡛ࡁࡿ᪂ࡓ࡞་⏝ศᏊࢩࢫࢸ࣒

“Lyotropic࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࡿࠋ

Zwitterionic Diblock Copolymer Aqueous Solutions”,

Morphology

TransitionofDouble

Macromol. Chem. Phys., 222, 2000377 (2021).
ㅰ㎡ᮏ◊✲ࡣࠊබ┈㈈ᅋἲே ᚨᒣ⛉Ꮫᢏ⾡᣺⯆㈈ᅋ
2020 ᖺᗘ◊✲ຓᡂࢆཷࡅ࡚⾜ࢃࢀࡲࡋࡓࠋරᗜ┴❧኱ 㐟బ┿୍෸ᩍᤵ࡜ࡢඹྠ◊✲࡛࠶ࡾࠊ࢝ࣝ࣎࢟ࢩ࣋ࢱ࢖࣓ࣥࢱࢡ࣮ࣜࣞࢺࣔࣀ࣐࣮ࡣ኱㜰᭷ᶵ໬Ꮫᕤ
ᴗᰴᘧ఍♫ ⊷ΏḠᖾẶ࡟ࡈᥦ౪࠸ࡓࡔࡁࡲࡋࡓࠋ
SAXSᐃ ࡣ SAGA-LS BL11 㸦 ㄢ 㢟 ␒ ྕ 㸸

No.1909074Fࠊ1911111Fࠊ2003020F㸧
࡟࡚ SagaLSἙᮏṇ⚽Ặ࡟ࡈᨭ᥼࠸ࡓࡔࡁᐇ᪋ࡉࢀࡲࡋࡓࠋᮏ◊✲ࢆࡈᨭ᥼ࢆ࠸ࡓࡔࡁࡲࡋࡓⓙᵝ࡟ᚰࡼࡾᚚ♩⏦ࡋୖࡆࡲࡍࠋ 