ಽሶဳⶄวಽሶߩ㓏ጀ⊛⒎ᐨ᭴ㅧߣࡑࠢࡠ⋧ಽ㔌࠳ࠗ࠽ࡒࠢࠬ 㧔ฬฎደᄢቇᎿቇ⎇ⓥ⑼㧕᧻ਅ ⑲ ޤߦߓߪޣ ࡉࡠ࠶ࠢ㊀ว߇ᒁ߈ߎߔ࠽ࡁ⋧ಽ㔌᭴ㅧߪ᧚ᢱߩ㜞ᯏ⢻ൻߦߟߥ߇ࠆ߽ߩߢࠆߚ ޔᄙ᭽ߥⷰὐ߆ࠄߩᄙߊߩ⎇ⓥ߇ߥߐࠇߡࠆ⎇ߩࠄࠇߎޕⓥߪ⚿ޟวߩޠ᭴▽ࠍ ೨ឭߣߒߡㅴࠄࠇߡߚ৻ޕᣇޔㄭᐕߢߪ㕖⚿ว㧔ߚߣ߃߫᳓⚛⚿ว㧕ㇱࠍዉߒ ߡห⒳ಽሶ߹ߚߪ⇣⒳ಽሶࠍળวߐߖޔಽሶࠍ᭴▽ߔࠆߎߣߦᄢ߈ߥ㑐ᔃ߇ነߖࠄࠇߡ ࠆࡁ࠽ߢߎߘޕ᭴ㅧࠍ⊒ߔࠆࡉࡠ࠶ࠢ㊀วߩࡉࡠ࠶ࠢ⚿วὐࠍ᳓⚛⚿วࠗࠝࡦ⚿ว ߣߔࠇ߫⚿ߩߘޔวജߪᲧセ⊛ᒙߩߢᄖㇱೝỗߦࠃߞߡ࠽ࡁ᭴ㅧߩࠝࡦࠝࡈಾࠅᦧ߃߇น ⢻ߥ㜞ᯏ⢻ᕈ᧚ᢱߣߥࠆߣᦼᓙߢ߈ࠆ(Fig.1)⎇ᧄޕⓥߢߪ㧞ߟߩᚻᴺߢࡐࡑᧃ┵ࠍ᳓⚛ ⚿วߢߟߥ߉ࠊߖࠆߎߣߦࠃߞߡࡉࡠ࠶ࠢࡐࡑဳಽሶ(ࡉࡠ࠶ࠢဳಽሶ)ࠍ⺞ߒޔ ᄖㇱೝỗߦࠃࠆ⚿ว⸃ⵚ߆ࠄࡑࠢࡠ⋧ಽ㔌⽎ࠍᒁ߈ߎߒࠍࠬࠢࡒ࠽ࠗ࠳ߩߘޔㅊ߁ߎߣ ࠍ⋡⊛ߣߒߡࠆޕ ⚿ޣᨐߣ⠨ኤޤ 㧝㧕ᧃ┵ࠢࠝ࠴࠼ဳࡐࡑ߆ࠄߩ᭴ㅧ᭴▽ߣ⸃ⵚ ࡉࡠ࠶ࠢဳⶄวಽሶߩ᭴ᚑಽሶߣߒߡࠝࠧࠢࠝ࠴࠼ᧃ┵ࡐࡑวᚑᴺߦߟߡ ᬌ⸛ߒቯ㊂⊛ᚻᴺࠍ⏕┙ߒߚౕޕ⊛ߦߪࡅ࠼ࡠࠠࠪ࡞ၮᧃ┵ࡐࡑߦੱᎿ DNA วᚑᴺߢ ࠆ Phosphoramidite ᴺࠍㆡ↪ߒߡⴕߞߚߩߎޕᣇᴺߪ Phosphoramidite(R2NP(OR)2)ߣࡅ࠼ࡠࠠ ࠪ࡞ၮ(-OH) ࠍଦㅴߦࠃߞߡ❗วߐߖ ߚ߈ߢޔphosphite(P(OR)3)ࠍ㉄ൻߐߖߡ phosphate (O=P(OR)3)ࠍᓧࠆ㉄ߦࠄߐޕಣℂߦࠃߞߡ⣕⼔ࠍⴕޔౣ߮ࡅ࠼ࡠࠠࠪ࡞ၮࠍᓧߡⶄᢙߩ ࠢࠝ࠴࠼ࠍዉߒߡߊᣇᴺߢࠆ┵ᧃࡑࡐޕ᭴ㅧߩ⏕ቯ㊂ߩߚߦࡐࡑ ਥ㎮ㇱಽࠍ㊀᳓⚛ൻߒߚౕޕ⊛ ߦߪ߹ߕಽሶ㊂ 1 ਁ⒟ᐲߩනಽᢔ ߥࡅ࠼ࡠࠠࠪ࡞ᧃ┵ࡐࠬ࠴ࡦ PTMSS-T3 NQI+ CW -d8 ࠍวᚑߒߦࠄߐޔ⸥ᔕࠍ➅ ࠅߔߎߣߦࠃߞߡ Thymidine ߇ 5 ߹ߢߟߚࡐࡑ(T5)ࠍᓧ ߚߡߟߦࠇߎޕṁᇦࠠࡖࠬ࠻ࠍ PS-A3 blend ⴕޔㅘㆊဳ㔚ሶ㗼ᓸ㏜ߣዊⷺ X ✢ᢔੂࠍ↪ߡ᭴ㅧⷰኤࠍⴕߞߚ ⚿ᨐ࠼࠴ࠝࠢࠧࠝޔㇱࠍ ࠪࡦ࠳ߣߒߚⷙೣ⊛ߥ࠽ࡁ⋧ ಽ㔌᭴ㅧ߇ⷰኤߢ߈ߚޕ1) ⛯ߡ(ࡦ࠴ࠬࡐޔPS), ࡐ 㧔㧠í࠻ࡔ࠴࡞ࠪ࡞ࠬ࠴ࡦ㧕 (PTMSS) ฦࡐࡑᧃ┵ߦ⋧ ⊛ߥࠢࠝ࠴࠼ࠍ 3 ߟߕߟዉ blend / inhibitor Figure 1. Schematic illustrations for formation of a diblock-type supramacromolecule via hydrogen bonding and its dissociation into componets by adding an inhibitory agent. SPO Figure 2. SAXS results for homopolymers and blends. The top curve is for PTMSS-T3, the second one for PS-A3, the third one for the blend of two polymers, and the bottom one for the blend of two polymers and an inhibitor. ߔࠆߎߣߦᚑഞߒߚౕޕ⊛ߦߪ PTMSS ߦߪ࠴ࡒࠫࡦࠍ 3 ߟޔPSd8 ߦߪ࠺ࠝࠠࠪࠕ࠺ࡁࠪ ࡦࠍ 3 ߟዉߒߚ┵ᧃޕዉ₸ߪ 1H-NMR ߢቯߒ߷߶ޔቯ㊂⊛ߦዉߐࠇߡࠆߎߣࠍ⏕ ߒߚ ࠍࡑࡐߩࠄࠇߎޕ1:1 ߢࡉࡦ࠼ߒߚṁᶧਛߢߩേࠍ 1HNMR ࠍ↪ߡⷰኤߒޔ ࠴ࡒࠫࡦߩࠗࡒ࠼ࡊࡠ࠻ࡦࡇࠢߩૐ⏛႐ࠪࡈ࠻ࠍ᷹ⷰߒߚ ߦࠄߐޕTEM ߦࠃߞߡࡃ࡞ࠢߢ ߩ࠽ࡁ⋧ಽ㔌᭴ㅧ߇ⷰኤߢ߈ ޔSAXS ߢ߽࠽ࡁ᭴ㅧᒻᚑߦ↱᧪ߔࠆ࿁᛬ࡇࠢ߇ࠄࠇߚߎ ߣ߆ࠄဳࠢ࠶ࡠࡉޔಽሶߩᒻᚑߦᚑഞߒߚ(Fig.2) ޕ2) ߹ߚ㒖ኂ࿃ሶࠍᛩਈߒߚṁᶧߩ 1 H-NMR ᷹ቯߢߪࠗࡒ࠼ࡊࡠ࠻ࡦࡇࠢ߇㜞⏛႐ࠪࡈ࠻ߒߡ߅ࠅޔ᳓⚛⚿วߩ㒖ኂ߇⏕ߐ ࠇߚޕ 㧞㧕ᧃ┵ቭ⢻ၮߩࠗࠝࡦ⚿วߦࠃࠆ᭴ㅧ᭴▽ ࠬ࡞ࡎࡦ㉄ߣ৻⚖ࠕࡒࡦ㑆ߦ↢ߓࠆࠗࠝࡦᕈ⋧↪ࠍ↪ߡࡉࡠ࠶ࠢဳಽሶ㧔Fig.3㧕 ࠍ⺞ߒࡁ࠽ߩߘޔ᭴ㅧⷰኤࠍⴕ߁ߎߣߣߒߚౕޕ⊛ߦߪ᭴ᚑࡉࡠ࠶ࠢߩࡉࡦ࠼Ყߩᓇ 㗀ߦߟߡ⺞ᩏߒߚࡦࠝ࠾ࠕࠣࡦࡆޕ㊀วᴺߦࠃࠅࠬ࡞ࡎࡦ㉄ᧃ┵ࡐࠬ࠴ࡦ 㧔PS-SO3H㧕ߣ৻⚖ࠕࡒࡦᧃ┵ࡐࠗ࠰ࡊࡦ (a) (b) 㧔PI-NH2㧕ࠍวᚑߒߚޕ೨⠪ߩಽሶ㊂ߪ 18k ߢޔ ᓟ⠪ߩಽሶ㊂ߪ 15㨗ߢߞߚ ߡߒߘޕPS-SO3H ߣ PI-NH2 ࠍหᤨߦ࠻࡞ࠛࡦߦṁ⸃ߒޔ2㨪3 ᣣ 㑆⒟ᐲ߆ߌߡṁᇦࠠࡖࠬ࠻ߒߚ ߦࠄߐޕ3 ᣣ㑆ޔ 120͠ߢࠕ࠾࡞ࠍⴕߞߚߩ⤑࠻ࠬࡖࠠߩߎޕ TEM ⷰኤߣዊⷺ X ✢ᢔੂ᷹ቯࠍⴕߞߚޕ㔚㗼ⷰ 50nm 200nm Figure 3. TEM images for the blend of : (a) 3/1; (b) 1/1. ኤ↪⹜ᢱߪࠝࠬࡒ࠙ࡓ㉄ࠍ↪ߡᨴ⦡ߒߚߚޔ ࡐࠗ࠰ࡊࡦㇱߦᒝࠦࡦ࠻ࠬ࠻߇ߟߊޕ 18kPS-SO3H /15kPI-NH2 Fig. 3 ߦߪ PS-SO3H ߣ PI-NH2 ߣߩഀว߇ 3:1 ᭴ㅧ߇ⷰኤߐࠇߡߎߣ߆ࠄ⚿ࡦࠝࠗޔวᕈࡉ ࡠ࠶ࠢဳಽሶࠍᒻᚑߒߡࠆߣ⠨߃ࠄࠇࠆޕ Fig.4 ߦߪઁߩᷙวᲧߩ߽ߩߣวࠊߖ X ✢ዊⷺ NQI+ CW ߢࠆࡉࡦ࠼ߩ㔚㗼౮⌀ࠍ␜ߒߡࠆࡔޕ 3:1 2:1 ᢔੂߩ࿁᛬ࡄ࠲ࡦࠍ␜ߔޕᷙวᲧ߇㆑ߞߡ߽ 1:1 1:2 ࡔ᭴ㅧࠍ᭴▽ߒߡࠆߎߣ߇ࠊ߆ࠆߩߎޕ ࠃ߁ߦ PS-SO3H ߣ PI-NH2 ࠍࡉࡦ࠼ߔࠆߣޔ ᧃ┵㑆ߩࠗࠝࡦᕈ⋧↪ߦࠃߞߡࡉࡠ࠶ࠢဳ ಽሶ߹ߚߪࠣࡈ࠻ဳಽሶ߇ᒻᚑߐࠇࠆޕ 1:3 SPO Figure 4. Comparison of SAXS profiles for blends. ޤ⺰⚿ޣ ੑߟߩಽሶ⸳⸘ᚻᴺ߆ࠄࡉࡠ࠶ࠢࠣࡈ࠻ ဳಽሶߩ᭴▽ߦᚑഞߒޔᄖ႐ߦࠃࠆ᭴ㅧᓮߩ⎇ⓥߩၮ⋚߇ߢ߈ߡࠆޕ ޣෳ⠨ᢥ₂ޤ 㧔 㧝 㧕 Noro, A.; Nagata, Y.; Tsukamoto, M.; Hayakawa, Y.; Takano, A.; Matsushita, Y. Biomacromolecules 2005, 6, 2328-2333. 㧔㧞㧕Noro, A.; Nagata, Y.; Takano, A.; Matsushita, Y. Biomacromolecules 2006, 7, 1696-1699.
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