ppb ࡟ࡌ࡞ߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦ⃻႐ಽᨆ↪࠽ࡁࠦࡦࡐࠫ࠶࠻଻ᜬ⤑ߩ㐿⊒⎇ⓥઍ⴫⠪ 㐳ጟᛛⴚ⑼ቇᄢቇ↥ቇⲢว࠻࠶ࡊ࡜ࡦ࠽࡯㙃ᚑ࠮ࡦ࠲࡯
↥ቇⲢว․છಎᢎ᝼ 㜞ᯅ↱♿ሶ㧝㧚✜⸒ ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߪ‫ޔ‬ㄭᐕߢߪ RoHS ᜰ઎ߥߤߢ‫ޔ‬㔚ᳰ߿ߪࠎߛ‫᧚ࠠ࠶ࡔޔ‬ᢱߣߒߡߩ૶↪ߪᕆỗߦᷫߞߚ߽ߩߩ‫ޔ‬ඨዉ૕߿ࠞ࠼ࡒ࠙ࡓࠗࠛࡠ࡯ߥߤߩ㗻ᢱߢᧂߛ૶↪ߐࠇߡ߅ࠅ‫ޔ‬ߎࠇࠄߩ὾ළ߿੝㋦ߩ♖㍰ᚲ߆ࠄ਎⇇ో૕ߢᐕ㑆 3 ਁ࠻ࡦ߽᡼಴ߐࠇߡ޿ࠆ‫ޕ‬WHO ߢߪ㘶ᢱ
᳓ਛ 3 ppb ߣቯ߼ࠄࠇ 1)‫ޔ‬ᣣᧄߢ߽ⅣႺၮḰߣߒߡ 10 ppb‫ޔ‬ឃ᳓ၮḰߣߒߡ 100 ppb2)ߣߐࠇߡ
޿ࠆ‫ੱޕ‬૕߳ߪਥߦ㘩ຠࠍㅢߓߡ៨ขߐࠇ‫ߪ∛ࠗ࠲ࠗࠗ࠲ࠗߦ․ޔ‬ᄙߊߩੱߩ⍮ࠆߣߎࠈߢ
޽ࠅ‫ߦࠄߐޔ‬ㄭᐕߢߪ⊒߇ࠎᕈ߽ᜰ៰ߐࠇߡ޿ࠆ 3,4㧕‫ⷙޕ‬೙୯࡟ࡌ࡞ߢߩࠞ࠼ࡒ࠙ࡓߪ‫⁁⃻ޔ‬ߢߪ ICP ⊒శಽᨆᴺ߽ߒߊߪ ICP ⾰㊂ಽᨆᴺߢⴕࠊࠇߡ߅ࠅ 5)‫ޔ‬ಽᨆߦ৻ㅳ㑆એ਄‫࠻ࠬࠦޔ‬߽㜞ߊ‫߫߃଀ޔ‬Ꮏᬺឃ᳓ߩ࠴ࠚ࠶ࠢ߿࿯ფᵞᵺࡊ࡜ࡦ࠻ߢߩㄦㅦߥ⹏ଔߣ޿߁ࠃ߁ߥᣣᏱ⊛ߥ᳓⾰▤ℂ߿‫ޔ‬㜞Ớᐲߩࠞ࠼ࡒ࠙ࡓߦᳪᨴߐࠇߚ☨߿㊁⩿‫ޔ‬᳓↥‛ߩㆬ೎‫ߪߦࠄߐޔ‬࿾⃿ⷙᮨߢߩᳪᨴߩታᘒᛠីߥߤߦߪ૶↪ߢ߈ߥ޿‫ޕ‬̌⺕ߢ߽࡮◲න࡮቟ଔߦ࡮ߘߩ႐ߢߢ߈ࠆ̍ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩ⃻႐ಽᨆᴺ߇᳞߼ࠄࠇߡ޿ࠆ‫ޕ‬ ㄭᐕ‫ޔ‬ᚒ‫ߪޘ‬㊄ዻࠗࠝࡦࠍኻ⽎ߣߒߚ‫ࡁ࠽ࠆߥࠄ߆࠻࠶ࠫࡐࡦࠦࡁ࠽ߪߊߒ߽ࡁ࠽⚛⦡ޟ‬⭯⤑⹜㛎⚕‫⎇ߩޠ‬ⓥࠍㅴ߼ߡ޿ࠆ 6-8)‫⹜ᧄޕ‬㛎⚕ߪ‫᦭ޔ‬ᯏᲧ⦡⹜⮎ߩ࠽ࡁ☸ሶ߽ߒߊߪ࠽ࡁࠦࡦࡐࠫ࠶࠻߇ࡈࠖ࡞࠲࡯ߩ㕙ߩߺߦᢙ⊖ nm㨪3 Pm ߩ⭯⤑ߣߒߡዪ࿷ߔࠆ⭯⤑᭴ㅧࠍߣࠆߚ߼‫ࠍࡦࠝࠗ࠻࠶ࠥ࡯࠲ߦߎߎޔ‬㜞ỚᐲߦỚ❗ߔࠆߎߣ߇น⢻ߢ‫ࠣࠪߡో߼ߚ޿⭯ߦࠄߐޔ‬࠽࡞߇ᬌ಴น⢻ߣߥࠆ‫ޕ‬ᣢሽߩ⹜㛎⚕߇᦭ᯏ⹜⮎ࠍỹ⚕ߥߤߩᡰᜬ૕ߦ฽ᶐߐߖߚ᭴ㅧߢ޽ࠆߚ߼ࠪࠣ࠽࡞߇Ꮧ㉼ߐࠇ‫ޔ‬ᗵᐲ߇ᢙච ppm ߦߣߤ߹ࠆߩߦኻߒ‫⹜ᧄޔ‬㛎⚕ߪ 3-4 ᩴ߽㜞ᗵᐲߢ޽ࠆ‫ޕ‬૞⵾ᣇᴺ߽◲ଢߢ‫᦭ޔ‬ᯏᲧ⦡⹜⮎ߩ࠽ࡁಽᢔᶧࠍ⋡ߩ⚦߆ߥࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ߢࠈㆊߔࠆߛߌߢ޽ࠆ‫ޕ‬ട߃ߡᧄ⹜㛎⚕ߢߪ‫߇⮎⹜ޔ‬࿕⋧ߣߒߡሽ࿷ߔࠆߚ߼ṁ಴߇ߥߊ߆ߟㅢᶧᕈ߇޽ࠆߚ߼‫࡞ࡊࡦࠨޔ‬ṁᶧࠍㅢᶧߔࠆߎߣߢ‫ߩࡦࠝࠗ࠻࠶ࠥ࡯࠲ࠆߥࠄߐޔ‬Ớ❗࡮㜞ᗵᐲൻ߇น⢻ߢ޽ࠆ㧔ㅢᶧỚ❗ᴺ㧕‫ޕ‬ ᧄ⎇ⓥߢߪࠞ࠼ࡒ࠙ࡓ↪ߩᲧ⦡⹜⮎ߣߒߡ‫ޔ‬࿑㧝ߦ␜ߔ᳓ṁᕈࡐ࡞ࡈࠖ࡝ࡦ TMPyP (Į,ȕ,Ȗ,į-Tetrakis (1-methylpyridinium-4-yl) porphine)ࠍ
↪޿‫☸ࡁ࠽ࠞ࡝ࠪߣࠇߎޔ‬ሶߣߩ࠽ࡁࠦࡦࡐࠫ࠶࠻⤑ࠍ૞⵾ߒߚ‫ޕ‬࿑㧞ߦ૞⵾ᣇᴺࠍ␜ߔ߇‫ޔ‬ၮᧄ⊛ߦߪਛᕈ߆ࠄࠕ࡞ࠞ࡝ᕈߢ⴫㕙߇⽶ߦᏪ㔚ߒߚࠪ࡝ࠞ࠽ࡁ☸ሶߩ⴫㕙ߦ 9)‫ࡦࠝࠗޔ‬੤឵ߦࠃࠅࠞ࠴ࠝࡦᕈߩ
TMPyP ࠍ଻ᜬߐߖ‫⴫ࠅࠃߦࠇߎޔ‬㕙ߩ࠯࡯࠲㔚૏߇ᷫዋߒߚࠪ࡝ࠞ☸ሶ߇ಝ㓸ߒ‫ࡦࠦࡁ࠽ޔ‬㧙㧙ࡐࠫ࠶࠻ࠍᒻᚑߔࠆ‫ߢ࡯࠲࡞ࠖࡈࡦ࡟ࡉࡦࡔࠍࠇߎޕ‬ỹㆊߔࠆߎߣߢ TMPyP/ࠪ࡝ࠞ࠽ࡁࠦࡦࡐࠫ࠶࠻⭯⤑ጀࠍ଻ᜬߒߚᬌ಴⤑ࠍ૞⵾ߔࠆ‫ޕ‬ᚑ⤑᧦ઙߩᦨㆡൻߣ⤑ߩࠠࡖ࡜ࠢ࠲࡝࠯࡯࡚ࠪࡦ‫ߩߣࡦࠝࠗࡓ࠙ࡒ࠼ࠞ߮ࠃ߅ޔ‬෻ᔕߩᦨㆡൻ‫ޔ‬ᅹኂߩᬌ⸛ࠍⴕߞߚߩߢߎࠇࠍႎ๔ߔࠆ‫ޕ‬㧞㧚ታ㛎
2.1 TMPyP/ࠪ࡝ࠞ࠽ࡁࠦࡦࡐࠫ࠶࠻଻ᜬ⤑ߩ૞⵾
 3.1 ߩ⴫㧝ߦ 5 ⒳㘃ߩࠗࠝࡦ੤឵૕ߣߒߡ↪޿ߚࠪ࡝ࠞᓸ☸ሶ㧔ᣣើ⸅ᇦൻᚑᩣᑼળ␠⵾㧕ࠍ␜ߔ߇‫ޔ‬USBB-120, F-120 ߪਇቯᒻ‫ޔ‬SI-350, SI-550, SA ߪ⃿ᒻߢ‫☸ޔ‬ᓘ߽ߘࠇߙࠇ⇣ߥࠆ‫ޕ‬
2 mM ߩ TMPyP ᳓ṁᶧ 100 Pl ߣ 4 × 10n5 wt% ߩࠪ࡝ࠞࠍ pH ⺞ᢛߐࠇߚ᳓ 10 mL ਛߢᷙวߒ‫ޔ‬ߎࠇࠍሹᓘ 0.1 Pm ߩ࠮࡞ࡠ࡯ࠬᷙวࠛࠬ࠹࡞࠲ࠗࡊࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯㧔ࠕ࠼ࡃࡦ࠹࠶ࠢ
␠⵾‫ޔ‬ሹᓘ 0.1 Pm ෘߐ 110Pm‫⋥ޔ‬ᓘ 47 mm㧕ߢๆᒁࠈㆊߒ⵾⤑ߒߚ‫⴫ߚ߹ޕ‬㧝ਛߩhalf[TMPyP/SA]ߦߟ޿ߡߪ TMPyP ߅ࠃ߮ SA ߩ㊂ࠍਔᣇߣ߽ඨಽߦߒ૞⵾ߒߚ‫ޕ‬
2.2 ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩᬌ಴
 TMPyP/ࠪ࡝ࠞ࠽ࡁࠦࡦࡐࠫ࠶࠻଻ᜬ⤑ࠍ⋥ᓘ 25 mm ߩ౞ᒻߦࠞ࠶࠻ߒ‫࠳࡞ࡎ࡯࠲࡞ࠖࡈޔ‬࡯ߦ᜽߻‫ࠍࡦࠝࠗࡓ࠙ࡒ࠼ࠞߦߎߎޕ‬฽߻ pH 10.2㧔὇㉄-὇㉄࠽࠻࡝࠙ࡓ✭ⴣᶧ㧕ߦ⺞ᢛߒ
ߚ 100 ml ߩࠨࡦࡊ࡞ṁᶧࠍ‫ޔ‬ᓴⅣᑼࠕࠬࡇ࡟࡯࠲࡯ߩ᳓᷷ࠍ಄ළེߦߡ 20°C ߩ৻ቯߣ଻ߟ
ߎߣߢ 4.05.0 mL min1 ߩ৻ቯㅦᐲߢㅢᶧߒߚ‫ޕ‬
2.3 ⵝ⟎ TMPyP/ࠪ࡝ࠞ࠽ࡁࠦࡦࡐࠫ࠶࠻ߩ☸ᓘߪേ⊛శᢔੂ㧔DLS㧕ߦߡ㧔ᄢႦ㔚ሶ ELSZ-2㧕‫⤑ޔ‬ߩᯏ᪾⊛ᒝᐲߪ㋦╩⎬ᐲ⹜㛎 (JIS K5600-5-4)‫ߩ⤑ޔ‬෻኿ๆశࠬࡍࠢ࠻࡞ߪశࡈࠔࠗࡃࠍⵝ⌕ߒߚ⍍㑆᷹శࠪࠬ࠹ࡓߦߡ㧔ᄢႦ㔚ሶ MCPD-3700㧕‫ߩ⤑ޔ‬ᢿ㕙ⷰኤߣࠪ࡝ࠞߩర⚛ಽᏓߦߪࠛࡀ࡞ࠡ࡯ಽᢔᒻ X ✢ಽశེ㧔EDX, Horiba EMAX㧕ࠍⵝ⌕ߒߚ㔚ሶ㗼ᓸ㏜㧔FE-SEM, ᣣ┙
S-800㧕ࠍ↪޿‫ޔ‬ᚑ⤑ᤨߩ TMPyP ߩ᝝㓸₸ߩ▚಴ߦ⚡ᄖนⷞಽశశᐲ⸘㧔ፉᵤ UV-1800㧕‫ࠞޔ‬࠼ࡒ࠙ࡓࠗࠝࡦߣߩ⊒⦡ࠍቯ㊂ൻߔࠆ㓙ߦ TLC ࠬࠠࡖ࠽࡯㧔ፉᵤ CS-9300PC㧕ࠍ↪޿‫࠼ࠞޔ‬ࡒ࠙ࡓࠗࠝࡦቯ㊂ߩ⹏ଔߣߒߡ ICP ⾰㊂ಽᨆⵝ⟎㧔ᣣᧄಽశ JMS-PLASMAX2㧕ߦߡ‫ࠇߘޔ‬ߙࠇ᷹ቯࠍⴕߞߚ‫ޕ‬㧙㧙㧟㧚⚿ᨐߣ⠨ኤ
3.1 ᚑ⤑᧦ઙߩᦨㆡൻ
(1) TMPyP/ࠪ࡝ࠞ࠽ࡁࠦࡦࡐࠫ࠶࠻଻ᜬ⤑ߩ૞⵾ ࠽ࡁࠦࡦࡐࠫ࠶࠻ߩ↢ᚑࠍ⏕⹺ߔࠆߚ߼‫ޔ‬2 × 105 M ߩ TMPyP ߣ 4 × 105 wt%ߩࠪ࡝ࠞ SA ࠍ pH 7.8 ߢᷙวߒߚᷙวᶧߣ 4 × 104 wt%ߩ SA ṁᶧߩ DLS ᷹ቯࠍⴕߞߚ⚿ᨐࠍ࿑㧟ߦ␜ߔ‫ޔࠅࠃࠇߎޕ‬ᢙචnm ߩ SA ☸ሶߦኻߒ‫ޔ‬ᷙวᶧߢߪ 100 nmࠍ⿥߃ࠆࠃࠅᄢ߈ߥಝ㓸૕߇㕒㔚⋧੕૞↪ߦၮߠ޿ߡ↢ߓߡ޿ࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬૶↪ߒߚࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ߩሹᓘ߇
0.1 Pm ߢ޽ࠆߩߢ‫ޔ‬SA ⥄૕ߪቯ㊂⊛ߦ᝝㓸ߐࠇߥ޿߇‫ޔ‬TMPyP/SA ࠽ࡁࠦࡦࡐࠫ࠶࠻ߪ߶߷ 100%᝝㓸ߐࠇࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬૞⵾ߒߚ⤑ߩᢿ㕙࿑ࠍ࿑㧠ߦ␜ߔ‫ޕ‬ᡰᜬ૕ߢ޽ࠆࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ߩ਄⴫㕙ߩߺߦ‫ޔ‬TMPyP/SA ࠽ࡁࠦࡦࡐࠫ࠶࠻⭯⤑ጀ߇޽ࠆߎߣ߇ࠊ߆
ࠆ‫ޕ‬EDX ߦࠃࠆ⤑ో૕ߩᢿ㕙ಽᨆߢ߽‫࡯࠲࡞ࠖࡈࡦ࡟ࡉࡦࡔߪࠞ࡝ࠪޔ‬ਛߦᬌ಴ߐࠇߕ‫࠽ޔ‬ࡁࠦࡦࡐࠫ࠶࠻ጀߩߺߦሽ࿷ߔࠆߎߣࠍ⏕⹺ߒߚ‫ޕ‬half[TMPyP/SA]࠽ࡁࠦࡦࡐࠫ࠶࠻ጀߩ⤑ෘߪᐔဋ 2.60 µm (n = 8, 15% RSD)ߢ‫ޔ‬TMPyP ߩ⴫㕙Ớᐲߪ 1.04 × 10n8 mol cmn2 ߢ޽ߞߚ‫ޕ‬(2) ࠪ࡝ࠞߩㆬቯ ⚿ᨐࠍ⴫㧝ߦ␜ߔ߇‫ޔ‬㋦╩⎬ᐲ⹜㛎ߩ⚿ᨐ‫ޔ‬TMPyP ߣࠪ࡝ࠞߩ ㊂ ࠍ ඨ ಽ ߣ ߒ ߚhalf-[TMPyP/SA]߇ 4H ߣᦨ߽⤑ߩᒝᐲ߇޽ࠅ‫ޔ‬ᜰߢߎߔߞߡ߽ߪ߇ࠇߥ޿⒟ᐲߢ޽ࠆ‫⹜ࠅࠃࠇߎޕ‬㛎⚕ߣߒߡߩ⢻ജࠍᄬࠊߥ޿⒟ᐲߦ‫ߊ⭯ޔ‬૞⵾ߔࠆᣇ߇᦭೑ߢ޽ࠆߎߣ߇ࠊ߆ࠆ‫ ߚ߹ޕ‬TLC ࠬࠠࡖ࠽ߢߩ 420 nm ߩࠞ࡜࡯ࡊࡠࡈࠔࠗ࡞߆ࠄ‫⴫ޔ‬㕙ߩᐔṖߐߪ‫ߩߘޔ‬ᮡḰ஍Ꮕ㧔S.D.㧕߆ࠄ USBB ߽ߒߊߪ SA ߇⦟޿ߎߣ߇ಽ߆ࠆ㧔TLC ࠬࠠࡖ࠽ߢߩ࠺࡯࠲ណขᣇᴺߪ࿑ 9(b)ෳᾖ㧕‫ ߚ߹ޕ‬3.2 ߦ␜ߔ߇‫ޔ‬20 ppb ߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩᬌ಴ߦ㑐ߒߡ‫ޔ‬TLC ࠬࠠࡖ࠽ߢߩ 485nm ߩⓍಽᒝᐲࠃࠅ‫ޔ‬half[TMPyP/SA]߇․ߦᄢ߈ߥ୯ࠍ␜ߒ‫᦭ޔ‬೑ߢ޽ࠆߎߣ߇ࠊ߆ࠆ‫⮎⹜ߪࠇߎޕ‬㊂߇ඨಽߦߥࠆߎߣߢࡃ࠶ࠢࠣ࡜࠙ࡦ࠼ߩ⹜⮎ߩๆ෼߇ᷫࠅ‫ࡓ࠙ࡒ࠼ࠞޔ‬-TMPyP ㍲૕ߩ✛⦡߇ࠃࠅ㞲᣿ߣߥߞߚߚ߼ߣ⠨߃ࠄࠇࠆ‫ޕ‬㧙㧙

(3) pH ߩᓇ㗀 TMPyP/SA ⤑૞⵾ᤨߩ pH ߩᓇ㗀ߦߟ޿ߡ‫ޔ‬pH 2-10 ߩ▸࿐ߢ⺞ߴߚ㧔࿑㧡㧕‫ޕ‬․ߦ pH 6.8-7.8 ߢߪ 99.8%ߩ TMPyP ߇ቯ㊂⊛ߦ଻ᜬߐࠇߚ‫ޕ‬ၮᧄ⊛ߦߪ‫ࠞ࡝ࠪޔ‬࠽ࡁ☸ሶߩ⴫㕙ߩ࠯࡯࠲㔚૏ߦଐሽߒ‫ޔ‬╬㔚ὐ pH0 1.8-2.2 ߆ࠄ pH ߇਄߇ࠆߦߟࠇߡ⴫㕙ߩ࠯࡯࠲㔚૏߇ࡑࠗ࠽ࠬߩᄢ߈޿୯ߦߥࠆߚ߼ 9)ߢ޽ࠅ‫ߢࡦࠝ࠴ࠞޔ‬޽ࠆ TMPyP ߇ๆ⌕ߐࠇ߿ߔߊߥࠆ‫ޕ‬pH10 ࠍ⿧߃ࠆߣࠪ࡝ࠞߩṁ⸃ߩߚ߼‫ޔ‬
TMPyP ߩ᝝㓸₸߇ਅ߇ࠆ‫ޕ‬(4) TMPyP ߣ SA ߩ㊂Ყߩᓇ㗀 ࿑㧢ߦ‫ޔ‬SA ㊂ࠍ৻ቯߣߒߚᤨߩ TMPyP ㊂ߩᓇ㗀㧔࿑ 6a㧕‫߮ࠃ߅ޔ‬ㅒߣߒߚ႐ว㧔࿑ 6b㧕ߩᓇ㗀ࠍ␜ߔ‫ޕ‬TMPyP ߩ㊂߇Ⴧ߃ࠆߣ TMPyP ߩ᝝㓸₸߽਄߇ࠅ‫[ޔ‬TMPyP/SA]ߢߪ 2-3 × 10n5M‫ޔ‬half[TMPyP/SA]ߢߪ 1 × 10n5 M ߢ‫ޔ‬99.9%ߩ TMPyP ߇᝝㓸ߐࠇ‫ޔ‬ቯ㊂⊛ߦ⤑߇૞⵾ߢ߈ࠆߎߣ߇ಽ߆ࠆ‫ࠇߘޔߒ߆ߒޕ‬એ਄ TMPyP Ớᐲ߇਄᣹ߔࠆߣㅒߦ᝝㓸₸ߪਅ߇ࠆ‫ߪࠇߎޕ‬TMPyP ㊂߇Ⴧ߃ࠆߣ‫ޔ‬TMPyP ಽሶ߇ࠪ࡝ࠞ☸ሶߩ⴫㕙ߦㆊ೾ߦๆ⌕ߒߚ⁁ᘒߣߥࠅ‫ోޔ‬૕ߣߒߡ࠯࡯࠲㔚૏߇ᱜߩᄢ߈޿୯ࠍᜬߟࠃ߁ߦߥࠆߚ߼ߢ‫ޔ‬ᱜߦᏪ㔚ߒߚ☸ሶห჻߇෻⊒ߒว޿‫ޔ‬ᄢ߈ߥಝ㓸૕ࠍ↢ߓߦߊߊߥࠆ‫⚿ޕ‬ᨐ‫ޔ‬TMPyP ㊂߇ᄙ޿႐วߪࡈࠖ࡞࠲࡯ߩሹ߆ࠄṳࠇ಴ߒߡߒ߹޿‫ޔ‬᝝㓸₸߇ਅ߇ࠆߣ⠨ኤߒߚ‫ ߚ߹ޕ‬SA ㊂ߩᓇ㗀߽ห᭽ߢ޽ࠅ‫ޔ‬ቯ㊂⊛ߥ⵾⤑߇น⢻ߥᦨㆡᷝട㊂ߪ‫ޔ‬TMPyP ߇ 2 × 10n5 M‫ޔ‬SA ߪ 4-6 × 10n5 wt%ߢ޽ߞߚ‫ޕ‬㧙㧙

(5) ࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ߩሹᓘߩᓇ㗀 TMPyP/SA ⤑૞⵾ᤨߩᡰᜬ૕ߣߒߡ‫ޔ‬0.1, 0.2, 0.45, 0.65, 0.8, 1.0 µm ߩሹᓘࠍ᦭ߔࠆࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ࠍ⹜ߺߚ‫ޕ‬⚿ᨐ‫ޔ‬0.1㨪0.65 µm ߹ߢߪ TMPyP ߩ᝝㓸₸ߪ 99.8%‫ޔ‬0.8 µm ߢ 99.7%‫ޔ‬
1.0 µm ߢ 99.6%ߣᄢ߈ߥሹᓘߩࡔࡦࡉ࡟ࡦࡈࠖ࡞࠲࡯ߢ߽ቯ㊂⊛ߥ૞⵾น⢻ߢ޽ࠆߎߣ߇ࠊ
߆ߞߚ‫ޕ‬࿑㧟ߩ☸ᓘಽᏓࠃࠅ߽ᄢ߈ߥሹᓘߩࡈࠖ࡞࠲࡯ߢ߽᝝㓸ߐࠇߡ޿ࠆߎߣ߆ࠄ‫⤑⵾ޔ‬ߩ㓙ߪ࠽ࡁࠦࡦࡐࠫ࠶࠻ห჻߇ߐࠄߦಝ㓸ߒߡ޿ࠆߎߣ߇␜ໂߐࠇࠆ‫ޕ‬
3.2 ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߣߩ෻ᔕ(1) ෻ᔕ pH ߩᓇ㗀 3.1 ߢ૞⵾ߒߚ TMPyP/SA ࠽ࡁࠦࡦࡐࠫ࠶࠻⤑ߦߡ‫ޔ‬ㅢᶧỚ❗ᴺߢࠞ࠼ࡒ࠙ࡓࠗࠝࡦࠍᬌ಴ߔࠆߚ߼ߩ෻
ᔕ pH ᧦ઙࠍ 2-12 ߹ߢ⺞ߴߚ‫ޕ‬࿑㧣ߦߪ 20 ppb ߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦࠍ฽ࠎߛṁᶧ 100 ml ࠍㅢᶧߒߚ㓙ߩ[TMPyP/SA]⤑ߢߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩ᛽಴₸ߣㅢᶧᓟߦ⤑਄ߦᱷሽߒ
ߚ TMPyP% ࠍ ␜ ߔ ‫ ㉄ ޕ‬ᕈ ஥ ߢ ߪTMPyP/SA ࠽ࡁࠦࡦࡐࠫ࠶࠻⤑߆ࠄ
ߩ TMPyP ߩṁ಴߇᷹ⷰߐࠇ‫ ߩᤨ⤑⵾ߪࠇߎޔ‬pH ଐሽᕈ㧔࿑㧡㧕ߣห᭽ߢ޽ࠅ‫㉄ޔ‬ᕈ஥ߢߪࠪ࡝ࠞߩ⽶㔚⩄߇ᷫዋߔࠆߚ߼ߣ⠨߃ࠆ‫ޔߚ߹ޕ‬pH 10 ߦߡࠞ࠼ࡒ࠙ࡓ-TMPyP ㍲૕ߩ↢ᚑ߇ᦨ߽ᄙߊߥߞߡ޿ࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬pH 10 ߢ 20 ppb ߩࠞ࠼ࡒ࠙ࡓࠍ฽߻᳓ṁᶧߢߪ‫ޔ‬᳓㉄ൻ‛ࠗࠝࡦൻቇ⒳ CdOH+߅ࠃ߮ Cd(OH)2 ߩ቟ቯᐲቯᢙ߇ߘࠇߙࠇ logK1 = 3.9 ߣ logE2 = 7.210㧕߆ࠄ⸘▚ߔࠆߣ‫ޔ‬Cd2+ߦട߃ߡ CdOH+߇ఝ૏ߦሽ࿷ߔࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬ㅢᏱࡐ࡞ࡈࠖ࡝ࡦߣ㊄㧙㧙ዻࠗࠝࡦߣߩ㍲ᒻᚑ෻ᔕߪㆃ޿ 11)߇‫ޔ‬CdOH+ߪ Cd2+ߦᲧߴߡ㍲ᒻᚑ෻ᔕ߇ᣧߊ‫ ߼ߚߩߘޔ‬pH10 ߣ޿߁ࠕ࡞ࠞ࡝᧦ઙߢ‫ޔ‬⷗߆ߌ਄ࠞ࠼ࡒ࠙ࡓ-TMPyP ㍲૕ߩ↢ᚑ㊂߇Ⴧᄢߔࠆߣផኤߒߚ‫ޕ‬(2) ᵹㅦߩᓇ㗀 ࿑㧤ߦ 20 ppb ߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦࠍ฽ࠎߛṁᶧ 100 ml ࠍㅢᶧߒߚ㓙ߩ half[TMPyP/SA]⤑ߢߩ ICP-MSߦࠃࠆࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩ᛽಴₸ߣ TL㧯ࠬࠠࡖ࠽ߢߩ 485 nm ߩⓍಽᒝᐲߦኻߔࠆᵹㅦߩᓇ㗀ࠍ␜ߔ‫ޕ‬ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߣ TMPyP ߩ㍲ᒻᚑ෻ᔕߪᵹㅦ߇ᄢ߈ߊߥࠆߣᷫዋߒߡ޿ࠆߚ߼‫ޔ‬ߘࠇ߶ߤᣧߊߥ޿ߎ
ߣ߇␜ໂߐࠇࠆ‫ޔߚ߹ޕ‬ICP-MS ߇ᵹㅦߦᲧ଀ߒߡ᛽಴₸߇ᷫዋߔࠆߩߦኻߒ‫ޔ‬TLC ࠬࠠࡖ࠽ߢߪ 5 mlmin-1 ߹ߢߪᷫዋߒ‫ߩߘޔ‬ᓟߪ޽߹ࠅᷫዋߒߥ޿ߣ޿߁Ꮕ߇⷗ࠄࠇߚ‫ޕ‬ߎࠇߪ‫ޔ‬ICP-MS ߪታ㓙ߦ TMPyP/SA ⭯⤑ߦ᛽಴ߐࠇߚࠞ࠼ࡒ࠙ࡓࠍ␜ߒߡ޿ࠆ߇‫ޔ‬TLC ࠬࠠࡖ࠽ߪ⴫㕙ಽᨆߩߚ߼‫ߩ⤑ޔ‬ᷓߐᣇะߢᬌ಴ᗵᐲ߇⪭ߜߡࠁߊߚ߼ߢ޽ࠅ‫ޔ‬ᬌ಴ᣇᴺߩᏅࠍ␜ߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬࿑㧤ߩ਄ߦᮨᑼ⊛ߦ TMPyP/SA ⭯⤑ߢߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩ⒖േߩ᭽ሶ߇␜ߒߡ޽ࠆ߇‫ޔ‬ᵹㅦ߇ዊߐ޿߁ߜߪ TMPyP/SA ጀߩ਄ㇱߦࠞ࠼ࡒ࠙ࡓߩ㜞Ớᐲ㗔ၞߪሽ࿷ߔࠆ߇‫ޔ‬ᄢ߈ߊߥࠆߦߟࠇߡ㍲ᒻᚑ෻ᔕ߇ᣧߊߥ޿ߚ߼‫ޔ‬ᓢ‫ ߦޘ‬TMPyP/SA ጀߩౝㇱ‫ޔ‬ਅㇱߣࠞ࠼ࡒ࠙ࡓ߇⒖േߒߡࠁߊ‫ޕ‬એ਄ 2 ߟߩℂ↱ߦࠃࠅ‫ޔ‬TLC ࠬࠠࡖ࠽․᦭ߩᵹㅦߩ
ᓇ㗀߇⃻ࠇࠆߣ⠨߃ࠄࠇࠆ‫ߩⷞ⋡ޕ‬㓙߽ TLC ߣหߓ⴫㕙ಽᨆߦ޽ߚࠅ‫ޔ‬ቯ㊂ᤨߪห᭽ߦᵹㅦߩ೙ᓮ߇ᔅⷐߢ޽ࠅ‫ޔ‬4.48 ml min-1㧔0.1 MPa ਅ㧕ߢⴕ߁ߎߣߣߒߚ‫ޕ‬(3) ࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩᬌ಴ ࿑㧥a ߦ half[TMPyP/SA]⤑ߢߩ 100 ml ߩࠨࡦࡊ࡞ṁᶧߩㅢᶧỚ❗ᤨߩ⚿ᨐࠍ␜ߔ‫ޕ‬half[TMPyP/SA]⤑ߢߪ 1 ppb ߽⋡ⷞߢᬌ಴น⢻ߛߞߚߩߦኻߒ‫[ޔ‬TMPyP/SA]⤑ߢߪ 10 ppb ߇㒢⇇ߢ޽ߞߚ‫⴫ߪࠇߎޕ‬㧝ߦ޽ࠆࠃ߁ߦ‫ޔ‬TMPyP ㊂߇ᷫዋߔࠆߎߣߦࠃߞߡࡃ࠶ࠢࠣ࡜࠙ࡦ࠼ๆ෼߇ᷫዋߒߚߚ߼ߣ⠨߃ࠄࠇࠆ‫ޕ‬࿑㧥b ߦ TLC ࠬࠠࡖ࠽ߢߩ࠺࡯࠲ណขᣇᴺࠍ૬ߖߡ࿑␜ߒߚ‫ޕ‬TLC ࠬࠠࡖ࠽ࠍ↪޿ߡ‫ޔ‬1ޯ200 ppb ߹ߢߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩᬌ㊂✢ࠍ૞⵾ߒߚ߇‫ޔ‬I = 16506.44 (1 ̅ e -0.05C)㧔I: TLC ࠬࠠࡖ࠽ߩ 485 nm ߢߩⓍಽᒝᐲ‫ޔ‬c: ࠞ࠼ࡒ࠙ࡓࠗࠝࡦỚᐲ㧕ߣ޿߁ᦛ✢ߢ⴫ߐࠇ‫⋧ޔ‬㑐ଥᢙ r = 0.9929 ߢ޽ߞߚ‫ޕ‬8 ߟߩࡉ࡜ࡦ᷹ࠢቯߦၮߠ߈‫ޔ‬3V߆ࠄ᳞߼ߚᬌ಴㒢⇇ߪ 0.102 ppb ߢ޽ߞߚ‫ޕ‬10 ppb ߩ᷹ቯ♖ᐲߪ‫ޔ‬8 ࿁᷹ቯߢᮡḰ஍Ꮕ 0.628 ppb ߣ㧙㧙ߥߞߚ‫ޕ‬(4) ᅹኂߩᬌ⸛
 10 ppb ߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩቯ㊂ߦኻߒ‫ޔ‬ฦ⒳ⅣႺ᳓ਛߦ฽߹ࠇࠆࠗࠝࡦߣ TMPyPߣ㍲ᒻᚑߔࠆน⢻ᕈߩ޽ࠆࠗࠝࡦߩᓇ㗀ࠍ⺞ߴߚ‫࡞ࠞޕ‬ࠪ࠙ࡓࠗࠝࡦ‫ࡓ࠙ࠪࡀࠣࡑޔ‬ࠗࠝࡦ‫ޔࡦࠝࠗࡓ࠙࡝࠻࠽ޔ‬ࠞ࡝࠙ࡓࠗࠝࡦߦߟ޿ߡߪ‫ޔ‬1000 ୚㊂ᷝടߒߡ߽ᓇ㗀ߪߥ߆ߞߚ‫ޕ‬Ⴎൻ‛ࠗࠝࡦ‫⥇ޔ‬ൻ‛ࠗࠝࡦ‫ޔ‬὇㉄ࠗࠝࡦ‫⎣ޔ‬㉄ࠗࠝࡦ‫ࠝ࠾ࠕߩ╬ࡦࠝࠗ㉄ࡦ࡝ޔ‬ࡦ߽ 290,000㨪3,500,000 ୚ߣᄢ㊂ߦᷝടߒߡ߽ᓇ㗀ߪ⷗ࠄࠇߥ߆ߞߚ‫ޕ‬㋕(III)ࠗࠝࡦ‫ޔࡦࠝࠗࡓ࠙࠾ࡒ࡞ࠕޔ‬ࡑࡦࠟࡦࠗࠝࡦߦߟ޿ߡߪ‫╬ޔ‬㊂ߢߪᓇ㗀ߪߥ߆ߞߚ߇‫ޔ‬100 ୚㊂ᷝടߔࠆߣᅹኂ߇⹺߼ࠄࠇߚ‫ ߪࠇߎޕ‬3ߟߩࠗࠝࡦߣ߽ pH 10.2 ߢട᳓ಽ⸃ߒ‫ޔ‬᳓㉄ൻ‛ߩᴉᲚ߇↢ߓࠆߚ߼ߢ‫ޔ‬ታ㓙ߦㅢᶧỹㆊߩ㓙ߦᵹㅦ߇⪺ߒߊ⪭ߜߚ‫ޕ‬TMPyP/SA ⤑ߢㅢᶧỚ❗ߔࠆ೨ߦ೨ỹㆊߔࠆߎߣߢߎࠇࠄߩᴉ
Ლࠍ㒰෰ߒ‫ޔ‬100 ୚㊂ᷝടᤨߢߩᅹ
ኂࠍ࿁ㆱߔࠆߎߣ߇ߢ߈ߚ‫ޔࠄ߇ߥߒ߆ߒޕ‬TMPyP ߣ㍲ᒻᚑߔࠆߣႎ๔ߐࠇߡ޿ࠆ‫ޔ‬੝㋦ࠗࠝࡦ‫ޔ‬㋦ࠗࠝࡦ‫ޔ‬㌃(II)ࠗࠝࡦߦߟ޿ߡߪᷓೞߥᅹኂࠍ߽ߚࠄߒߚ‫ޕ‬2-ࠕࡒࡁࠛ࠲ࡦ࠴ࠝ࡯࡞‫ޔ‬2,3-ࠫࡔ࡞ࠞࡊ࠻-1-ࡊࡠࡄࡦࠬ࡞ࡎࡦ㉄‫࠻ࡊࠞ࡞ࡔޔ‬㈶㉄ߣ޿߁ 3 ߟߩࡑࠬࠠࡦࠣ೷ߦߡ㒰෰ࠍ⹜ߺߚ߇‫ޔ‬pH 10.2 ߢߪ࿎㔍ߢ޽ߞߚ‫ޕ‬࿑㧝㧜ߦ‫ޔࡦࠝࠗࡓ࠙ࡒ࠼ࠞޔ‬㋦ࠗࠝࡦ‫ޔ‬㌃ࠗࠝࡦߣ෻ᔕߐߖߚᓟߩ TMPyP/SA ⤑ߩࠬࡍࠢ࠻࡞ࠍ␜ߔ‫ޕ‬੝㋦ࠗࠝࡦߦߟ޿ߡ߽㧽ࡃࡦ࠼ߣ޿
߁ 550-700 nm ߩࡐ࡞ࡈࠖ࡝ࡦ․᦭ߩๆ෼Ꮺ߇㊄ዻߦࠃߞߡ⇣ߥߞߡ޿ࠆߎߣ߇ࠊ߆ߞߚ‫ߎޕ‬ࠇࠄࠗࠝࡦࠍታ㛎ᠲ૞ߢಽ㔌ߔࠆߎߣߪ࿎㔍ߢ޽ࠆ߇‫ޔ‬ᄙᵄ㐳หᤨಽᨆߦࠃࠅಽ㔌ߢ߈ࠆน⢻ᕈߪᱷߐࠇߡ޿ࠆߣ⸒߃ࠆ‫ޕ‬㧙㧙㧠㧚߹ߣ߼࡮ᧄᬌ಴⤑ߩቯ㊂⊛⵾⤑ߩᦨㆡ᧦ઙߪ‫ ߪࠞ࡝ࠪޔ‬SA㧔⃿ᒻ㧘10-14 nm㧕‫ޔ‬૞⵾ pH ߪ 6.8-7.8‫ޔ‬
TMPyP Ớᐲߪ 2 × 10n5 M‫ޔ‬SA Ớᐲߪ 4-6 × 10n5 wt%‫࡯࠲࡞ࠖࡈࡦ࡟ࡉࡦࡔޔ‬ሹᓘߪ 0.65 µm એਅߢ޽ߞߚ‫ޕ‬࡮half[TMPyP/SA]࠽ࡁࠦࡦࡐࠫ࠶࠻⭯⤑ߪ‫ޔ‬㋦╩⎬ᐲ⹜㛎ߢߩᒝᐲ᷹ቯߢ߽ 4H એ਄ߣߪ߇ࠇߦߊߊ‫ߩߘޔ‬ෘߐߪ 2.60 µm ߢဋ৻߆ߟ⴫㕙߽ᐔṖߢ޽ߞߚ‫ޕ‬࡮ᧄᬌ಴⤑ߢߩࠞ࠼ࡒ࠙ࡓࠗࠝࡦߩᬌ಴ᦨㆡ᧦ઙߪ‫ޔ‬pH 10.2‫ޔ‬ๆᒁ࿶ 0.1 MPa㧔4.48 ml min-1㧕ߢ޽ߞߚ‫ޕ‬࡮⋡ⷞߢ߽ 1 ppb ߇ᬌ಴น⢻ߢ‫ޔ‬TLC ࠬࠠࡖ࠽ߢߪᬌ಴㒢⇇ 0.102 ppb‫ޔ‬ቯ㊂਄㒢⚂ 200 ppb
ߢ޽ߞߚ‫ޕ‬࡮ࠕ࡞ࠞ࡝᧦ઙߢߩᬌ಴ߢ޽ࠆߚ߼‫ޔ‬TMPyP ߣߩ෻ᔕᕈ߆ࠄ੝㋦‫ޔ‬㋦‫ޔ‬㌃ࠗࠝࡦߩᅹኂ߇ㆱ
ߌࠄࠇߥ߆ߞߚ߇‫ࠇߘޔ‬એᄖߩᄙߊߩࠗࠝࡦߩᅹኂߪฃߌߥ߆ߞߚ‫ޕ‬⻢ㄉ ᧄ⎇ⓥߪ‫ޔ‬JFE21 ਎♿⽷࿅ߩᛛⴚ⎇ⓥഥᚑ㧔2008 ᐕᐲ㧕ߦࠃࠅታᣉߐࠇߚ߽ߩߢ޽ࠅ‫ޔ‬ᷓߊᗵ⻢⥌ߒ߹ߔ‫ޕ‬ෳ⠨ᢥ₂[1] World Health Organization, Guidelines for drinking-water quality, 3rd ed., incorporating 1st and2nd addenda, Vol.1, Geneva, 2008.
[2] http://www.cadmium.org/environment.html (International Cadmium Association).
[3] Lars Järup, British Medical Bulletin, Vol. 68 © The British Council (2003) 167–182.
[4] http://www.env.go.jp/en/water (Ministry of the Environment, Government of Japan).
[5] Ꮏ႐ឃ᳓⹜㛎ᴺ JIS K 010.
[6] Y. Takahashi, H. Kasai, H. Nakanishi, T. M. Suzuki, Angew. Chem., Int. Ed. 45 (2006) 913-916.
[7] Y. Takahashi, S. Danwittayakul, T. M. Suzuki, The Royal Society of Chemistry, Analyst 134(2009) 1380-1385.
[8] Y. Takahashi, T. M. Suzuki, Nanotechnology Applications for Clean Water, William Andrew,Norwich New York, 2009, Part 4, pp417-425.
[9] George A. Parks, Chem. Rev., 65 (1965) 177-198.
[10] Bunseki Kagaku Binran, fifth ed., Marzen, Tokyo, 2003, 648.
[11] K. Kawamura, S. Igarashi, T. Yotsuyanagi, Inorg. Chim. Acta 360 (2007) 3287-3295.

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