1P001᦭ᯏࡐ࡝ࡑ࡯ࡑ࠻࡝࠶ࠢࠬౝߢߩࠪࠢࡠࡈࠜࠬࡈࠔ࠯ࡦࠗࠝࡦᶧ૕ߩ⊒శ᜼േ㧔ችፒᄢᎿ࡮㧔ᩣ㧕ࡉ࡝࠵ࠬ࠻ࡦ 㧕٤ᑝἑ␽઩࡮⊕਄ ദ࡮᧻ᧄ ੳ࡮ᄢ᦬ᱜ⃨ ࡮଻↰᣽⑲
Emission Behaviors of Ionic Liquid Having Cyclophosphazene Moiety in Organic PolymerMatrix (Univ. of Miyazaki, Bridgestone Corporation*) HIROSE, Shogo; SHIRAGAMI,Tsutomu; MATSUMOTO, Jin; OTSUKI, Masashi*; YASUDA, Masahide

శ㊀วᕈࠫࠕ࠮࠴࡟ࡦ⢽⾰ߣ㕖㊀วᕈ⢽⾰߆ࠄߥࠆ⋧ಽ㔌ᷙวࡌࠪࠢ࡞ߩ⺞⵾㧔ችፒᄢᎿ㧕٤᧻ᧄ ੳ࡮⊕਄ ദ࡮଻↰᣽⑲
Preparation and characterization of phase-segregated mixed vesicles consisting ofpolymerizable diacetylene and non-polymerizable amphiphiles (Univ. Miyazaki)
MATSUMOTO, Jin; SHIRAGAMI, Tsutomu; YASUDA, Masahide1B01䇼ᐨ䇽㩷 ੑಽሶ⤑᭴ㅧ䉕᦭䈜䉎䊔䉲䉪䊦䈲䇮↢૕⤑䈱䊝䊂䊦䈫䈚䈩ᐢ䈒⎇ⓥ䈘䉏䈩䈇䉎䇯ੑಽሶ⤑ౝ䈪䈱⢽⾰ಽሶ䈱⋧ಽ㔌⁁ᘒ䉕೙ᓮ䈜䉎䈖䈫䈲䇮↢૕ᯏ⢻⸃ᨆ䈜䉎਄䈪㊀ⷐ䈪䈅䉎䇯ᧄ⎇ⓥ䈪䈲䇮శ㊀วᕈ䉳䉝䉶䉼䊧䊮ၮ䉕᦭䈜䉎䊖䉴䊐䉜䉼䉳䊦䉮䊥䊮(DTPC)䈮䇮䉝䊆䉥䊮ᕈ⢽⾰(2C16S)䈅䉎䈇䈲䉦䉼䉥䊮ᕈ⢽⾰(2CnN)䈱ᷙว䊔䉲䉪䊦䉕૞⵾䈚䇮ᒻᘒⷰኤ䈫ੑᚑಽ䈱ᷙว⁁ᘒ䈱⏕⹺䉕ⴕ䈦䈢[1]䇯䇼ታ㛎䇽㩷 䊔䉲䉪䊦ṁᶧ䈱⺞⵾䈲䇮એਅ䈱⭯⤑᳓๺(TFH)ᴺ䉕↪䈇䈩ⴕ䈦䈢䇯2CnS 䉁䈢䈲 2CnN䉕 DTPC 䈮䊝䊦Ყ 2:100 䈪ᷙว䈚䈢 CHCl3–MeOH ṁᶧ(0.1 mM)䉕䊐䊤䉴䉮䈮ណ䉍䇮ṁᇦ䉕⇐෰䈚䈢䇯䈖䉏䈮 HEPES ✭ⴣṁᶧ䉕ട䈋䇮80 °C 䈮䈩⿥㖸ᵄᾖ኿䈚䇮22.5 °C 䈪 3 ᣣ㑆㕒⟎䈚䇮⢽⾰Ớᐲ䈏 0.1 mM 䈱䊔䉲䉪䊦ṁᶧ䉕ᓧ䈢䇯ᰴ䈮䇮4 °C 䈪 1h ಄ළ䈚䇮254 nm 䈱⚡ᄖ✢ᾖ኿䈪㊀วOOO䈘䈞䈢䊔䉲䉪䊦䈱⥄ኅⰯశ䉕䇮౒ὶὐ䊧䊷䉱䊷㗼ᓸ㏜P(CH2)8OO
H(CH2)10O
H(CH2)10(CH2)8OH(CLSM)䈪ⷰኤ䈚䈢䇯⸃ᨆ⚿ᨐ䉕 Table 1 䈮␜䈜䇯ODTPCNMe3‫⚿ޣ‬ᨐߣ⠨ኤ‫ޤ‬DTPC ࠍ TFH ᴺߢಣℂߒ‫⚡ޔ‬ᄖ✢ࠍOOSO3Na H(CH2)n1 C Oᾖ኿ߒߚߣߎࠈ‫⋥ޔ‬ᓘ߇ 5.5 Pm ߩࠫࡖࠗࠕࡦ࠻ࡌࠪ H(CH2)n O
NMe2 IH(CH2)n1 C O
ࠢ࡞(GV, 1)߇ᓧࠄࠇߚ‫ޕ‬ᰴߦ‫ޔ‬2C16S ࠍ DTPC ߦᷙ H(CH2)n OOOวߒߚ߽ߩࠍห᭽ߦಣℂߒߡࡌࠪࠢ࡞(2)ࠍ⺞⵾ߒ
2C12S; n = 12
2C12N; n = 12 2C14N; n = 14
2C16S; n = 16
2C16N; n = 16ߚ‫ޕ‬2 ߩᢿጀⰯశ௝ࠍ CLSM ⸃ᨆߒߚߣߎࠈ‫⋥ޔ‬ᓘScheme 1.
3.8 Pm ߩ࡝ࡦࠣ਄ߦ‫ޔ‬1 Pm ߩᥧㇱࠍ᦭ߔࠆ᭴ㅧ૕߇
Table 1. The characterization of 1–6.
ᓧࠄࠇߚ‫ ࡦࡒ࠳࡯ࡠ࡞ࠪ࠺࠲ࠢࠝޕ‬B ࠍ 2 ߦᷙวߔF
Additional Diameter(%)
amphiphileࠆߣ‫ޔ‬ᥧㇱ߆ࠄ߽Ⱟశ߇ᓧࠄࠇߚߩߢ‫ޔ‬2C16S ߩ(Pm)–
4.5
24
1DTPC ߆ࠄߩ⋧ಽ㔌߇⏕⹺ߐࠇߚ‫ޕ‬ห᭽ߦ‫ޔ‬2C16N
2C16S
3.8
26
2
ࠍ DTPC ߦᷙวߔࠆߣ⋥ᓘ 3.7 Pm ߩ GV ߇ᓧࠄࠇ(4)‫ ޔ‬32C12S
4.0
17
2C16N
3.7
25
41 Pm ߩᥧㇱ߇ⷰኤߐࠇߚ‫৻ޕ‬ᣇ‫ޔ‬2C12S‫ޔ‬2C12N‫ޔ‬
2C14N
7.5
135
߹ߚߪ 2C14N ࠍ DTPC ߦᷙวߒߚ႐ว‫ޔ‬ౝㇱߩ⹣߹
2C12N
9.0
166
䈦䈢ળว૕(3, 5, 6)䈻䈫᭴ㅧ䈏ᄌൻ䈚䈢䇯㊀ว⁁ᘒ䉕⹏ଔ䈜䉎䈢䉄䇮1–6 䈱ๆ෼䉴䊕䉪䊃䊦䉕᷹ቯ䈚䇮䊘䊥䉳䉝䉶䉼䊧䊮ਥ㎮㛽ᩰ਄䈱᦭ല౒ᓎ㐳䈏㐳䈇ᚑಽ䈫⍴䈇ᚑಽ䈮↱᧪䈜䉎ๆ෼ᵄ㐳䈪䈱ๆశᐲ(A600, A485)䈱Ყ F = 100uA600/A485 䉕▚಴䈚䈢䇯2, 4 䈱 F ୯䈲 26%䈍䉋䈶 25%䈫䈭䉍䇮
1 䈱 F ୯(24%)䈫䈾䈿৻⥌䈚䈢䈖䈫䈎䉌䇮2C16S 䈍䉋䈶 2C16N 䈲䇮DTPC 䈫⋧ಽ㔌䈚䈢䉅䈱䈫⠨䈋䉌䉏䉎䇯৻ᣇ䇮3䇮5䇮6 䈱 F ୯䈲 20%એਅ䈫䈭䉍䇮1 䈱 F ୯䉋䉍䉅ᷫዋ䈚䈢䇯㕖㊀วᕈ⢽⾰䈏 DTPC䈫ᷙว䈜䉎䈖䈫䈪䇮౒ᓎ㐳䈱㐳䈇䉳䉝䉶䉼䊧䊮䈱㊀ว䈏ᅹ䈕䉌䉏䈢䉅䈱䈫⠨䈋䉌䉏䉎䇯 એ਄ߩߎߣ߆ࠄ‫ޔ‬ᷙวߔࠆ㕖㊀วᕈ⢽⾰ߩࠕ࡞ࠠ࡞㎮㐳ࠍᄌൻߐߖࠆߎߣߢ‫ޔ‬㊀ว૕
DTPC ࡌࠪࠢ࡞ߩ⋧ಽ㔌⁁ᘒ߅ࠃ߮ᒻᘒࠍ೙ᓮߢ߈ߚ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬[1] T. Shiragami, Y. Nakamura, J. Matsumoto, M. Ootsuki, M. Yasuda, Chem. Lett. 2010, 39, 1006.

[1] Matsumoto, K. Yoneda, J. Tasaka, T. Shiragami, M. Yasuda, Bull. Chem. So c. Jpn. 2010, 83, 1551.

Fluorescence‫ޓ‬Intensity/a.uR‫ޣ‬ᐨ‫ޤ‬ᚒ‫ࡦ࠯ࠔࡈࠬࡎ࡝࠻ࡠࠢࠪࡠࠝ࡞ࡈ࠲ࡦࡍޔߪޘ‬R +N R㛽ᩰࠍᜬߟࠕࡦࡕ࠾࠙ࡓࠞ࠴ࠝࡦߣࡆࠬ㧔࠻࡝ࡈ࡞ࠝࡠFO- OPࡔ࠲ࡦࠬ࡞ࡎ࠾࡞㧕ࠗࡒ࠼ࠕ࠾ࠝࡦ 6(5+ ߆ࠄ᭴ᚑߐࠇF3C S N S CF3NNOOࠆࠗࠝࡦኻൻว‛  ߇ࠗࠝࡦᶧ૕ߦߥࠆߎߣࠍ⷗޿ߛ FPP FNߒߡ޿ࠆ㧔࿑㧝㧕=?‫⊒ߪ  ߚ߹ޕ‬శᕈࠍ␜ߒ‫⊒ߩߘޔ‬శFF᜼േ߇  ߩળว⁁ᘒߣኒធߦ㑐ㅪߒߡ޿ࠆߣផ᷹ߒߡ޿
1a; R = -(CH2)8-H
1b; R = -(CH2)4-Hࠆ‫⎇ᧄޕ‬ⓥߢߪ‫᦭ޔ‬ᯏࡐ࡝ࡑ࡯ߣ  ߣߩⶄว૕ࠍ⺞⵾ߒ‫ޔ‬ࡐ࡝ࡑ࡯ࡑ࠻࡝࠶ࠢࠬౝߦ  ࠍ㐽ߓߎ߼ࠆߎߣ߇  ߩ⊒ Fig. 1 Chemical structure of 1శ᜼േߦኻߒߡ‫ߥ߁ࠃߩߤޔ‬ᓇ㗀ࠍ෸߷ߔ߆ߦߟ޿ߡᬌ⸛ߒߚ‫ޕ‬ ߣ 2//# RQN[OGVJ[NOGVJCCET[NCVG ߣߩⶄว૕ߩ⺞⵾ߪએਅߩᣇᴺߢⴕߞ‫ޣ‬ታ㛎‫ޤ‬ߚ‫ ޕ‬I㨪I ߣ 2//# I ࠍ฽߻ࠢࡠࡠࡎ࡞ࡓṁᶧ O. ࠍ㧞㧠ᤨ㑆ᝄߣ߁ߒ‫ޔ‬ߘߩᷙวṁᶧࠍࠟ࡜ࠬၮ᧼਄ߦဋ৻ߦႣᏓߒߚᓟ‫ޔ‬ᷫ࿶ੇ῎ߔࠆߎߣߢࡈࠖ࡞ࡓ⁁ߩⶄว૕ 2//# ࠍᓧߚ‫ޕ‬2//# ߩࠟ࡜ࠬォ⒖᷷ᐲ 6I
ߪ &5% ߦߡ‫⊒ޔ‬శࠬࡍࠢ࠻࡞ߪ౒ὶὐ࡟࡯ࠩ࡯Ⱟశ㗼ᓸ㏜ߦߡߘࠇߙࠇ᷹ቯࠍⴕߞߚ‫⚿ޣޕ‬ᨐߣ⠨ኤ‫⺞ ޤ‬⵾ߒߚ C2//#㧔C ߩ฽᦭₸ 㧑㧕ߩ౮⌀ࠍ࿑㧞ߦ␜ߔ‫ޕ‬C ߩ฽᦭₸߇㜞޿ߦ߽߆߆ࠊࠄߕ‫ⶄޔ‬ว૕ߩㅘ᣿ᐲߪቢోߦ଻ᜬߐࠇࠆߎߣ߇ࠊ߆ߞߚ‫ޕ‬C2//# ߩ 6I
Fig. 2 Photos of 1a/PMMA andࠍ᷹ቯߒߚߣߎࠈ‫ޔ‬C ߩ฽᦭㊂ߩჇട㧔㨪㧕ߦ઻PMMA޿‫ޔ‬6I ୯߇ ͠߆ࠄ ͠߹ߢ৻᭽ߦᷫዋߒߚ‫ࠄߐޕ‬ߦ D2//# ߦߟ޿ߡߪ‫ ߢ߹͠ޔ‬6I ߇ૐਅߒߚ‫ߩߎޕ‬1a(neat) ߣ 2//# ߣߩ⋧ṁᕈ㧔น႟ᕈ㧕߇ᄢ߈ߊะ਄ߎߣߪ‫ޔ‬
1a/PMMAߒߡ޿ࠆߎߣࠍ␜ߒߡ޿ࠆ‫ޕ‬ᰴߦ‫ޔ‬C2//# ߦ POߩ⚡ᄖ✢ࠍᾖ኿ߔࠆߣ‫ޔ‬㕍⦡⊒శ߇᷹ⷰߐࠇߚ‫ߩߘޕ‬ᤨߩ⊒శࠬࡍࠢ࠻࡞ࠍ࿑  ߦ␜ߔ‫ߢ࠻࡯࠾ޕ‬᷹ቯߒߚࠬࡍࠢ࠻࡞ߣᲧセߔࠆߣ‫ⶄޔ‬ว૕ߩࠬࡍࠢ࠻࡞ߢߪో૕⊛ߦ⍴ᵄ㐳஥߳ࠪࡈ࠻ߒߡ޿ࠆߎߣ߇ࠊ߆ߞߚ‫ޕ‬D
400500600ߢ߽ห᭽ߩ⚿ᨐ߇ᓧࠄࠇߚ‫ޔߪߣߎߩߎޕ‬ ߇ 2//#
Wavelength / nm ߩ Fig.3 Emission spectra of 1a/PMMAࡑ࠻࡝࠶ࠢࠬౝߦ㐽ߓߎ߼ࠄࠇࠆߎߣߦࠃߞߡ‫ޔ‬ળว⁁ᘒ߇ᄌൻߒߚߎߣࠍ␜ໂߒߡ޿ࠆ‫ޕ‬and neat 1a.

IS

1B01

Preparation and characterization of phase-segregated mixed
vesiclesconsisting
ofpolymerizable
diacetylene
andnon-polymerizable amphiphiles(Univ. Miyazaki) MATSUMOTO, Jin; SHIRAGAMI, Tsutomu; YASUDA,
MasahideIS

1B01

Preparation and characterization of phase-segregated mixed
vesiclesconsistingofpolymerizable
diacetylene
andnon-polymerizable amphiphiles(Univ. Miyazaki) MATSUMOTO, Jin; SHIRAGAMI, Tsutomu; YASUDA,
Masahide[Interoduction] For the modification of functionalized vesicles, the phase segregation ofvesicles has received much attention in order to elucidate the functions of signal transduction andmembrane transport of the vesicles. Here, we prepared binary component GVs containing aphosphatidyl choline with photopolymerizable diacetylene groups (PCDA) and a double-chain
anionic amphiphile (2CnS, n = 12, 16) or a cationic amphiphile (2CnN, n = 12, 14, 16) without
polymerizable group.
[Experimental] Vesicle solutions were prepared by modified thin-film hydration method. A
confocal laser scanning fluorescence microscope analysis was performed with an Olympus[Interoduction] For the modification of functionalized vesicles, the phase segregation ofvesicles has received much attention in order to elucidate the functions of signal transduction andmembrane transport of the vesicles. Here, we prepared binary component GVs containing aphosphatidyl choline with photopolymerizable diacetylene groups (PCDA) and a double-chain
anionic amphiphile (2CnS, n = 12, 16) or a cationic amphiphile (2CnN, n = 12, 14, 16) without
polymerizable group.
[Experimental] Vesicle solutions were prepared by modified thin-film hydration method. A
confocal laser scanning fluorescence microscope analysis was performed with an Olympus

FV–300 (confocal aperture = 150 µm, Japan) equipped with an objective lens (u 100 oil,numerical aperture = 1.3). A vesicle solution was placed in the hole of a silicon spacer (1 cm u1 cm, 50-µm thickness) on a slide glass and was enclosed with a cover glass.
OO
O[Results and Discussion]
A mixture of sodiumP(CH2)8OO
H(CH2)10O
H(CH2)10(CH2)8OH
1,2-di(hexadecyloxycarbonyl)ethanesulfonate(2C16S)
ODTPC
NMe3
with photopolymerizable 1,2-di(10,12-tricosadiynoyl)OO
SO3Na H(CH2)n1 C O
sn-glycerol 3-phosphocholine (DTPC) in a 2:100 ratio H(CH2)n O
NMe2 I
H(CH2)n1 C O
was treated by modified thin-film hydration to give an H(CH2)n O
OOaggregate which became polymerized giant vesicles
2C12S; n = 12
2C12N; n = 12 2C14N; n = 14
2C16S; n = 16
2C16N; n = 16(GVs) under irradiation at 254 nm. The autofluorescence
Scheme 1.
of the GVs was analyzed with a confocal laser scanning

FV–300 (confocal aperture = 150 µm, Japan) equipped with an objective lens (u 100 oil,numerical aperture = 1.3). A vesicle solution was placed in the hole of a silicon spacer (1 cm u1 cm, 50-µm thickness) on a slide glass and was enclosed with a cover glass.
OOO[Results and Discussion]
A mixture of sodium
P(CH2)8O
O
H(CH2)10
O
H(CH2)10(CH2)8OH
1,2-di(hexadecyloxycarbonyl)ethanesulfonate(2C16S)ODTPCNMe3
with photopolymerizable 1,2-di(10,12-tricosadiynoyl)OO
SO3Na H(CH2)n1 C O
sn-glycerol 3-phosphocholine (DTPC) in a 2:100 ratio H(CH2)n O
NMe2 IH(CH2)n1 C O
was treated by modified thin-film hydration to give an H(CH2)n OOOaggregate which became polymerized giant vesicles
2C12S; n = 12
2C12N; n = 12 2C14N; n = 14
2C16S; n = 16
2C16N; n = 16(GVs) under irradiation at 254 nm. The autofluorescence
Scheme 1.
of the GVs was analyzed with a confocal laser scanningmicroscope at the cross section, revealing a 3.8-Pm
diameter ring shape and the presence of a dark part of ca.

Table 1.

The characterization of 1–6.
F
Additional Diameter(%)
amphiphile
(Pm)
–
4.5
24
2C16S
3.8
26
2C12S
4.0
17
3.7
2C16N
25
2C14N
13
7.5
16
2C12N
9.0

microscope at the cross section, revealing a 3.8-Pm
diameter ring shape and the presence of a dark part of ca.

Table 1.

The characterization of 1–6.
F
Additional Diameter(%)
amphiphile
(Pm)
–
4.5
24
2C16S
3.8
26
2C12S
4.0
17
3.7
2C16N
252C14N
137.5
162C12N
9.0

11 Pm in the ring (Table 1). When octadecylrhodamine B
2(RhB) as an amphiphilic fluorescence probe was added to34
the GV, the fluorescence of RhB was emitted from the5whole ring. Therefore, phase segregation of 2C16S
6from DTPC was confirmed. Similarly, mixed vesicles of N,N-di(2-hexadecanoyloxyethyl)-

1
1 Pm in the ring (Table 1). When octadecylrhodamine B
2(RhB) as an amphiphilic fluorescence probe was added to34
the GV, the fluorescence of RhB was emitted from the5whole ring. Therefore, phase segregation of 2C16S
6from DTPC was confirmed. Similarly, mixed vesicles of N,N-di(2-hexadecanoyloxyethyl)-

dimethylammonium iodide with DTPC were found to be 3.7-Pm diameter phase-segregatedvesicles with a dark portion of ca. 1 Pm on the ring in the cross sectional image. On the other
hand, DTPC vesicles mixed with 1,2-di(dodecyloxycarbonyl)ethanesulfonate, N,N-di(2dodecanoyloxyethyl)dimethylammonium
iodide,andN,N-di(2-tetradecanoyloxyethyl)
dimethylammonium iodide formed sphere structures filling the inside of the vesicles. The
segregation mechanism was explained by the difference in the main phase transition temperatureof each amphiphile.

dimethylammonium iodide with DTPC were found to be 3.7-Pm diameter phase-segregatedvesicles with a dark portion of ca. 1 Pm on the ring in the cross sectional image. On the other
hand, DTPC vesicles mixed with 1,2-di(dodecyloxycarbonyl)ethanesulfonate, N,N-di(2dodecanoyloxyethyl)dimethylammonium
iodide,and
N,N-di(2-tetradecanoyloxyethyl)
dimethylammonium iodide formed sphere structures filling the inside of the vesicles. The
segregation mechanism was explained by the difference in the main phase transition temperatureof each amphiphile.

[1] Matsumoto, K. Yoneda, J. Tasaka, T. Shiragami, M. Yasuda, Bull. Chem. So c. Jpn. 2010, 83, 1551.

[1] Matsumoto, K. Yoneda, J. Tasaka, T. Shiragami, M. Yasuda, Bull. Chem. So c. Jpn. 2010, 83, 1551.