Title 毛髪の物性解析及び脂質分布、動態に関する研究( 本文(Fulltext) ) Author(s) 髙橋, 俊江 Report No.(Doctoral Degree) 博士(工学) 連創博甲第28号 Issue Date 2015-03-25 Type 博士論文 Version ETD URL http://hdl.handle.net/20.500.12099/51020 ※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。
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ẟ㧥ࡢ≀ᛶゎᯒཬࡧ⬡㉁ศᕸࠊ
ືែ㛵ࡍࡿ◊✲
Analyses of physical property,
lipid-distribution and -dynamics
in human hair
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ᗎㄽ
4 㡫
➨㸯❶ ẟ㧥⬡㉁◊✲
7 㡫
㸯㸫㸯㸬⬡㉁ࡣ
8 㡫
㸯㸫㸰㸬ẟ㧥ࡣ
14 㡫
㸯㸫㸱㸬ẟ㧥ࡢ⬡㉁
21 㡫
㸯㸫㸲㸬┠ⓗ
26 㡫
㸯㸫㸳㸬᪉ἲ
27 㡫
㸯㸫㸴㸬⤖ᯝ
36 㡫
㸯㸫㸵㸬⪃ᐹ
59 㡫
㸯㸫㸶㸬⤖ㄽ
63 㡫
➨㸰❶ ẟ㧥≀ᛶ◊✲ 64 㡫
㸰㸫㸯㸬⫼ᬒ
65 㡫
㸰㸫㸰㸬┠ⓗ
66 㡫
㸰㸫㸱㸬᪉ἲ
67 㡫
㸰㸫㸲㸬⤖ᯝ
75 㡫
㸰㸫㸳㸬⪃ᐹ
83 㡫
㸰㸫㸴㸬⤖ㄽ
87 㡫
3 / 106
➨㸱❶ ᚋࡢᒎᮃ
88 㡫
ཧ⪃ᩥ⊩
89 㡫
ㅰ㎡
100 㡫
◊✲ᴗ⦼┠㘓
102 㡫
4 / 106
ᗎㄽ
18 ୡ⣖༙ࡤጞࡲࡗࡓ⏘ᴗ㠉ࡼࡾẟ⧊≀⏘ᴗࡀᛴ⃭Ⓨᒎࡋࠊࡑ ࡢᚲせᛂࡌ࡚ୡ⏺୰࡛⨺ẟࡢ◊✲ࡀⓎᒎࡋࡓࠋࢽ࣮ࣗࢪ࣮ࣛࣥࢻࡢ WRONZ㸦Wool Research Organization of New Zealand Inc.㸧ࠊࢻࢶࡢ DWI㸦Deutsche Wollforschungs Institut㸧ࠊ࣮࢜ࢫࢺࣛࣜࡢ CSIRO 㸦Commonwealth Scientific and Industrial Research Organisation㸧࡞ ࡀᑓ㛛ⓗ࡞◊✲ᶵ㛵ࡋ࡚ᣲࡆࡽࢀࡿࠋ⏘ᴗᛂ⏝⛉ᏛࡢほⅬࡽ⨺ẟࡢ ᵓ㐀ࡸ≀ᛶࡀ⢭ᰝࡉࢀࠊᅜ㝿ⓗ࡞Ꮫࡀᐃᮇⓗ㛤ദࡉࢀ ࡚⌧ᅾࡶ⥆࠸࡚ ࠸ࡿࠋࣄࢺẟ㧥◊✲ࡢṔྐࡣ⨺ẟࡼࡾࡶὸࡃ ࠊேࠎࡢ⏕άỈ‽ྥୖక࠺ 㤶⢝ရ⏘ᴗࡢⓎ㐩ࡶ◊✲ᑐ㇟ࡋ࡚ὀ┠ࡉࢀ ጞࡵࡓࠋ20 ୡ⣖༙ࡤ ࡣࠊඛ⾜ࡋ࡚࠸ࡓ⨺ẟ◊✲࡛ᇵࢃࢀࡓ◊✲ᇶ┙ࢆ⏝ࡋ࡚ࠊ⨺ẟྠᵝ ⧄⥔ࡋ࡚ࡢᵓ㐀ࡸ≀ᛶ࡞ẟ㧥ࡑࡢࡶࡢࡢ≉ᛶࡢ◊✲ࡀ┒ࢇ⾜ࢃࢀ ࡓࠋᙜࡢඛ㥑ⓗ◊✲⪅࡛ẟ㧥◊✲ࡢᩍ⛉᭩ⓗ࡞ᴗ⦼ࢆࡶࡓࡽࡋࡓ Robbins ࡸ Swift ࡽࡣᜥ㛗ࡃ⌧ᅾࡶ◊✲ࢆ⥆ࡅ࡚࠸ࡿࠋ ẟ㧥⛉Ꮫࡣேࠎࡢ⨾ព㆑ࡸ⏕ά⩦័ࡢኚ㑄ᛂ࠼࡞ࡀࡽࡑࡢ◊✲ㄢ㢟 ࢆࢩࣇࢺࡉࡏ࡚࠸ࡁࠊእほࠊឤゐࠊࢫࢱࣝ࡞ឤぬ㛵ࢃࡿ◊✲Ⓨ ᒎࡋࡓࠋࡑࢀక࠸ࠊึᮇࡣᏛ࡛⨺ẟ◊✲ࡢ୍㒊ࡋ࡚ᢅࢃࢀ࡚࠸ࡓ ẟ㧥◊✲ࡀ㤶⢝ရ⛉Ꮫࡢ୰୍࡛㒊㛛ࢆ⠏ࡁࠊInternational Hair-Science
SymposiumࠊApplied Hair Science Conference ࡞ࠊẟ㧥◊✲≉ࡋ ࡓᅜ㝿㆟ࡀ㛤ࢀࡿࡲ࡛⮳ࡗࡓࠋ㏆ᖺ࡛ࡣ◊✲ࡢࢸ࣮࣐ࡀ࢚ࢪࣥࢢࠊ ⫱ẟࠊே✀◊✲࡞ࠊẟ㧥ࢆ⏕యࡢ୍㒊ࡋ࡚ᤊ࠼ࡓ⏕άᐇឤᛂ࠼ࡿࡶ ࡢࢫࢸ࣮ࢪࢆ⛣ࡋ࡚ࡁࡓឤࡀ࠶ࡿࠋ
5 / 106 ࢆࡶࡘჾᐁ࡛࠶ࡿࠋ㢌⓶ࡼࡾࡶእฟࡓ㒊ศࢆẟᖿࠊෆධࡗࡓ㒊ศࢆ ẟ ᰿࠸࠺ࠋẟᖿࡣ┤᥋እ⏺᥋ࡍࡿ࠸࠺Ⅼ࡛ࠊ⏕యࡢࡢ⤌⧊ࡣ␗࡞ ࡿ㠀ᖖ≉Ṧ࡞⎔ቃ࠶ࡿࠋࡋࡋࠊゅࡋࡓ⣽⬊ࡽᡂࡿࡓࡵ⏕ᶵ⬟ ࢆᣢࡓࡎࠊእ⏺ࡽࡢ่⃭ࡼࡗ࡚ᦆയࡋ࡚ࡶ⮬ࡽᅇ ࡍࡿࡣ࡛ࡁ࡞࠸ࠋ ่⃭ࡼࡿᦆയᣲືࡶྵࡵࡓẟᖿࡢᵝࠎ࡞≉ᛶࡣࠊẟ᰿ୗ㒊ࡢẟ⌫࡛⏕ྜ ᡂࡉࢀࡓⅬ࡛Ỵᐃࡉࢀ࡚࠸ࡿࠋ ከࡃࡢẟ㧥࢚ࢪࣥࢢ◊✲ࡼࡾຍ㱋కࡗ࡚ẟ㧥ࡢ≉ᛶࡀኚࡍࡿ ࡀሗ࿌ࡉࢀ࡚࠾ࡾࠊࡑࡢከࡃࡣឤゐࡸእほࡢຎࢆࡶࡓࡽࡍࡶࡢ࡛࠶ࡿࠋ ࡋࡋࠊࡑࡢ≉ᛶኚࡣᚲࡎࡋࡶ୍ᵝ㐍ࡴࢃࡅ࡛ࡣ࡞ࡃࠊ࠶ࡿᖺ௦࠾ ࠸࡚ಶேᕪࡀᴟࡵ࡚ࡁࡃࡤࡽࡘࡁࢆぢࡏࡿ≀ࡀ࠶ࡿࠋࡑࡢࡼࡾࠊ➹⪅ ࡣẟ㧥ࡢ⏕ྜᡂࡢ㐣⛬࡛ẟ⌫ෆ࠾࠸࡚ຍ㱋ࢆ㐍ࡵࡿࠊࡲࡓࡣ㏫ᢠࡍࡿ ࢫࢵࢳࡀാࡃሙྜࡀ࠶ࡿࡢ࡛ࡣ࡞࠸⪃࠼ ࡚࠸ࡿࠋ ⬡㉁ࡣ⏕యࡗ࡚࢚ࢿࣝࢠ࣮※ࠊ⤌⧊ᵓ⠏ᡂศࠊ⏕⌮ᶵ⬟ㄪ⠇࡞ከ ᵝ࡞ാࡁࢆࡍࡿࠋẟ㧥࠾࠸࡚ࡶእ࡛ࡣ࡞ࡃࠊ⬡㉁ࡣẟ㧥⤌⧊ࡢᵓ⠏ࠊ ࣂࣜᶵ⬟⥔ᣢࠊ⢓ᙎᛶࡸ₶ᛶࡢⓎ⌧ຍ࠼࡚ࠊẟ⌫࠾ࡅࡿ⏕ྜᡂᶵ ᵓࡢㄪ⠇ࡗ࡚ࡶ㠀ᖖ㔜せ࡞ᙺࢆᯝࡓࡋ࡚࠸ࡿࠋ๓㏙ࡋࡓຍ㱋ኚ ᢠࡍࡿ⤌ࡳ⬡㉁ࡀ㛵ࡍࡿྍ⬟ᛶࡣᑠࡉࡃ࡞࠸ࠋࡋࡋ⌧Ⅼ࡛ࡣࠊ ⏕ྜᡂ㐣⛬࠾ࡅࡿẟ㧥⬡㉁ࡢලయⓗ࡞ᶵ⬟ゎ᫂ᚲせ࡞▱ぢࡣࠊ⬡㉁ࡢ ศᕸࠊᵓ㐀ࠊືែࡢ ࠸ࡎࢀࡘ࠸࡚ࡶ༑ศࡣᚓࡽࢀ࡚࠸࡞࠸ࠋ ᮏ◊✲࠾࠸࡚ࡣࠊࡲࡎẟ㧥ࡢᚤ⣽ᵓ㐀࡛ࣞ࣋ࣝࡢ⬡㉁ࡢศᕸࡸ௦ㅰ ࡘ࠸࡚◊✲ࢆ㐍ࡵࠊẟ㧥⏕ྜᡂࡢ⤌ࡳ㛵ࡍࡿ⬡㉁ࡢᙺゎ᫂ࡢ➃⥴ࢆ 㛤ࡃࢆ┠ᣦࡋࡓࠋḟ࠸࡛ẟ㧥ࡢຍ㱋క࠺≉ᛶኚࡋ࡚࣮࢟ࣗࢸࢡ ࣝࡢᦆയᣲືࢆྲྀࡾୖࡆࡓࠋ ᮏㄽᩥࡣ௨ୗࡢ 2 ⦅ࡢཎⴭㄽᩥࢆᇶࡋ࡚సᡂࡋࡓࠋ
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ㄽᩥ㸸Takahashi T, Yoshida S (2014) Distribution of Glycolipid and
Unsaturated Fatty Acids in Human Hair. Lipids 49:905-917
ㄽᩥ㸸Takahashi T, Mamada A, Breakspear S, Itou T, Tanji N (2015)
Age-dependent changes in damage processes of hair cuticle. Journal of Cosmetic Dermatology 14:2-8
ㄽᩥࡢෆᐜࢆ➨㸯❶ࠊㄽᩥࡢෆᐜࢆ➨㸰❶࡛ᢅࡗࡓࠋᮏㄽᩥ࠾࠸ ࡚ཎⴭㄽᩥࡽࡢᅗ⾲ࡢᘬ⏝ࡣࠊฟ∧♫ࡽࡢチྍࢆᚓࡓࡶࡢ࡛࠶ࡿࠋ
7 / 106
➨㸯❶ ẟ㧥⬡㉁◊✲
8 / 106
㸯㸫㸯㸬⬡㉁ࡣ
⬡㉁ࡣᏛᵓ㐀࡛ࡣ࡞ࡃᛶ㉁ ᇶ࡙࠸࡚ᐃ⩏ࡉࢀࡿࠋBloor ࡢ⥲ㄝ 㸦1925 ᖺ㸧[1] ࠾࠸࡚ࠊ⬡㉁ࡢᐃ⩏ศ㢮ࡣ௨ୗࡢᵝ࡞ࡉࢀࡓࠋ 㹙ᐃ⩏㹛 㹟㸬Ỉ⁐ࡘ࢚࣮ࢸࣝࠊࢡ࣒ࣟࣟ࣍ࣝࠊ࣋ࣥࢮࣥ࡞ࡢ⁐፹ྍ⁐ 㹠㸬⬡⫫㓟࢚ࢫࢸࣝࢆᙧᡂࡋ࡚࠸ࡿࡶࡋࡃࡣᙧᡂࡀྍ⬟ 㹡㸬⏕యࡼࡗ࡚⏝ࡉࢀࡿ 㹙ศ㢮㹛 ࣭༢⣧⬡㉁㸸Fat㸦⬡⫫㓟ࡢࢢࣜࢭ࣮࢚ࣟࣝࢫࢸࣝ㸧, Wax
࣭」ྜ⬡㉁㸸Phospholipid, Glycolipid, Aminolipid, Sulfolipid࡞
࣭ㄏᑟ⬡㉁㸦ୖグࡢ⬡㉁ࡢຍỈศゎ≀㸧㸸Fatty acid, Sterol
2014 ᖺཌ⏕ປാ┬ࡀหࡋࡓࠕ᪥ᮏேࡢ㣗ᦤྲྀᇶ‽㸦2015 ᖺ∧㸧ࠖ
⟇ᐃ᳨ウሗ࿌᭩ [2] ࡛ࡣ⬡㉁ࡢᐃ⩏ศ㢮ࡣḟࡢᵝグ㍕ࡉࢀ࡚࠸
ࡿࠋ
ࠕ⬡㉁㸦lipids㸧ࡣࠊỈ⁐࡛ࠊ᭷ᶵ⁐፹⁐ゎࡍࡿྜ≀࡛࠶ࡿࠋᰤ
㣴Ꮫⓗ㔜せ࡞⬡㉁ࡣࠊ⬡⫫㓟㸦fatty acid㸧ࠊ୰ᛶ⬡⫫㸦neutral fat㸧ࠊ
ࣜࣥ⬡㉁㸦phospholipid㸧ࠊ⢾⬡㉁㸦glycolipid㸧ཬࡧࢫࢸ࣮ࣟࣝ㢮㸦sterols㸧
࡛࠶ࡿࠋࠖ
ᮏㄽᩥ࡛ࡣࡇࢀࡽࡢᐃ⩏࣭ศ㢮ᚑ࠸ࠊࡘእᅉᛶࡢ⬡㉁ࡣ┬࠸࡚ࠊ ⏕య⏤᮶ࡢ⬡㉁ࡢࡳࢆᢅ࠺ࡶࡢࡍࡿࠋ
9 / 106 㸯㸫㸯㸫㸯㸬ᙺ [1-8] ⬡㉁ࡣ⏕యࡸ㣗ရྵࡲࢀࠊ⏕⌮స⏝≀㉁ࡋ࡚㠀ᖖ㔜せ࡞ᙺࢆ ᢸ࠺≀㉁࡛࠶ࡿࠋ⏕య✚ࡋࡓ⬡㉁ࡣ௦ㅰࡉࢀ࡚࢚ࢿࣝࢠ࣮ࢆ⏘⏕ࡋ ࡓࡾࠊࣅࢱ࣑ࣥࡸ࣍ࣝࣔࣥ࡞⏕⌮ᶵ⬟ㄪ⠇≀㉁ࡢ⏕ྜᡂࢃࢀࡿࠋ ࡲࡓࠊ⣽⬊ࡸ⣽⬊⭷ࡢᵓᡂᡂศࡋ࡚⏕యࡢ⤌⧊ࢆᵓ⠏ ࡍࡿࡶࠊ ⣽⬊ෆ㒊እ⏺ࡢሗఏ㐩ࠊእ⏺ᑐࡍࡿ㜵ᚚࠊ⏕ྜᡂ㐣⛬ࡢ㛵 ࡞ከᵝ࡞ᶵ⬟ࢆⓎࡍࡿࠋ እ⏺┤᥋ࡉࢀࡿ⎔ቃ࠶ࡿ⓶ẟ㧥ࡗ࡚ࠊ ⬡㉁ࡢ㜵ᚚᶵ⬟ ࡣ≉㔜せ࡛࠶ࡿࠋ ࡑࢀࡘ࠸࡚ࡣᚋ㏙ࡍࡿࠋ
10 / 106 㸯㸫㸯㸫㸰㸬」ྜ⬡㉁ [1-6] ࡢ≀㉁⬡㉁ࡀ⤖ྜࡋࡓࡶࡢࢆ」ྜ⬡㉁ࡧࠊࣜࣥ⬡㉁ࠊࢫࣇ ࣥࢦ⬡㉁ࠊ⢾⬡㉁࡞ࡀᣲࡆࡽࢀࡿࠋ ࡇࢀࡽࡣ⣽⬊⭷ࢆᙧᡂࡍࡿせ ࡞ᡂศ࡛࠶ࡿࠋ ࣜࣥ⬡㉁ࡣࣜࣥ㓟ࢆࣔࣀࡲࡓࡣࢪ࢚ࢫࢸࣝࡢᙧ࡛ྵࡴ⬡㉁࡛ࠊ ⣽⬊⭷ ࡢ⣙ 50% ࢆ༨ࡵࡿࠋࢢࣜࢭࣜࣥ㦵᱁ࢆ᭷ࡍࡿࢢࣜࢭࣟࣜࣥ⬡㉁ࡸࢫࣇ ࣥࢦࢩࣥࢆ㦵᱁ᣢࡘࢫࣇࣥࢦࣜࣥ⬡㉁ࡀ࠶ࡿࠋ ࣜࣥ⬡㉁ḟ࠸࡛ࢫࣇࣥࢦ⬡㉁ࡶࡲࡓ⣽⬊⭷ከࡃྵࡲࢀࠊ⣽⬊⾲ 㠃ࡢཷᐜయࡋ࡚ࡢᶵ⬟ࢆࡶࡘࠋ⓶ࡢ⣽⬊㛫⬡㉁ࡢᡂศࡢࢭ࣑ࣛࢻ ࡣ㛗㙐ࡢ࣑ࣀࣝࢥ࣮࡛ࣝ࠶ࡿࢫࣇࣥࢦ ࢩࣥ⬡⫫㓟ࡀ⤖ྜࡋࡓࡶ ࡢ࡛ࠊࢫࣇࣥࢦ⬡㉁ࡢ୍✀࡛࠶ࡿࠋ ⢾⬡㉁ࡣࢢࣝࢥ࣮ࢫࠊ࢞ࣛࢡࢺ࣮ࢫࠊN ࢭࢳࣝࢢࣝࢥࢧ࣑ࣥࠊN -ࢭࢳࣝ࢞ࣛࢡࢺࢧ࣑ࣥ࡞ࡢ༢⢾ࡀࢢࣜࢥࢩࢻ⤖ྜ࡛⬡㉁⤖ྜࡋࡓ ࡶࡢ࡛࠶ࡿࠋ⣽⬊⭷Ꮡᅾࡋ࡚Ᏻᐃࡉࡏࡓࡾࠊྜ≀ࡢㄆ㆑ࢧࢺ ࡋ࡚ാ࠸ࡓࡾࡍࡿࠋ⢾⬡㉁ࡣࡑࡢ㦵᱁ࡼࡗ࡚ࢢࣜࢭࣟ⢾⬡㉁ࠊࢫࢸࣟ ࣮ࣝ⢾⬡㉁ࠊࢫࣇࣥࢦ⢾⬡㉁ศ㢮ࡉࢀࡿࠋࢫࣇࣥࢦ⢾⬡㉁ࡢෆࠊ ࢩࣝ㓟ࢆྵ᭷ࡍࡿࡶࡢࢆ࢞ࣥࢢࣜ࢜ࢩࢻ࠸࠺ࠋࡇࢀࡣ⬻⚄⤒⣔ከ 㔞Ꮡᅾࡋࠊ⚄⤒⣔ࡢಟࠊ⣽⬊ࡢቑṪࠊࢩࢢࢼࣝఏ㐩ࠊ≀㉁ࡢࣞࢭࣉ ࢱ࣮࡞⣽⬊ᶵ⬟ࡢไᚚ㛵ࢃࡗ࡚࠸ࡿࠋ
11 / 106 㸯㸫㸯㸫㸱㸬㣬ࠊ㣬⬡⫫㓟 [1-5] ⬡⫫㓟ࡣ㔜⤖ྜࢆࡶࡓ࡞࠸㣬⬡⫫㓟㔜⤖ྜࢆ᭷ࡍࡿ㣬 ⬡⫫㓟ࡀ࠶ࡿࠋ๓⪅ࡣᏛⓗᏳᐃࡔࡀࠊᚋ⪅ࡣ㓟 ࡉࢀ᫆ࡃẚ㍑ⓗ Ᏻᐃ࡛࠶ࡿࠋ㣬⬡⫫㓟ࡢෆࠊ㔜⤖ྜࡀ୍ࡘࡢ≀ࡣ୍౯㣬⬡⫫ 㓟ࠊ」ᩘᏑᅾࡍࡿࡶࡢࡣከ౯㣬⬡⫫㓟 㸦PUFA㸧ࡤࢀࡿࠋᚋ⪅ ࡣ≉ᛂᛶࡀ㧗ࡃ࢚ࢿࣝࢠ࣮ ※ࠊ⣽⬊⭷ᵓᡂ≀㉁ࠊ⏕⌮ⓗάᛶ≀㉁࢚ ࢥࢧࣀࢻࡢཎᩱ࡞ࡿ࡞⏕యࡗ࡚㠀ᖖ㔜せ࡛࠶ࡿ ࠋࡲࡓࠊ ⏕య୰ࡢ㣬⬡⫫㓟ࡢ㔜⤖ྜࡣᇶᮏⓗ cis య࡞ࡢ࡛ࠊ㣬⤖ྜ ᩘࡀከ࠸ศᏊࡣᒅ᭤ࡋ࡚ࣂ࣮ࣝ࢟࡞ᵓ㐀࡞ࡿࠋ ⣽⬊⭷Ꮡᅾࡍࡿ ࣜࣥ⬡㉁ࡢ㣬⬡⫫㓟ࡣࡑࡢࣂ࣮ࣝ࢟ᛶࡢࡏ࠸࡛ ࣜࣥ⬡㉁ὶືᛶࢆ ࡋࠊ⤌⧊㛫ࡢ₶ᛶࢆቑࡍࠋ㣬⤖ྜࢆ 6 ࡘࡶᣢࡘࢻࢥࢧ࣊࢟ࢧ ࢚ࣥ㓟㸦DHA㸧࡞ࡣࡑࡢຠᯝࡀᴟࡵ࡚㧗࠸ࠋ⚄⤒⣽⬊ࡣ㍈⣴ࡸᶞ≧✺ ㉳࡞⭷ࡢྜࡀ㠀ᖖከ࠸ᵓ㐀࡛࠶ࡿࡀࠊDHA ࡀ⣽⬊⭷ࡢᰂ㌾ᛶࢆ ⥔ᣢࡋ࡚⬻࣭⚄⤒⣔ࡢᛶᐤࡋ࡚࠸ࡿࠋ 㣬⬡⫫㓟ࡢෆࠊ࣓ࢳࣝᇶᮎ➃ࡽᩘ࠼࡚᭱ึࡢ 㔜⤖ྜࡀ 3 ␒┠ ࠶ࡿ≀ࡣ n-3 ⣔ࡲࡓࡣ ω3ࠊ6 ␒┠࠶ࡿ≀ࡣ n-6 ⣔ࡲࡓࡣ ω6ࠊ9 ␒┠࠶ࡿ≀ࡣ n-9 ⣔ࡲࡓࡣ ω9 ศ㢮ࡉࢀࡿࠋࡑࢀࡒࢀࠊ௦⾲ⓗ࡞⬡ ⫫㓟ࡣ α ࣜࣀࣞࣥ㓟ࠊࣜࣀ࣮ࣝ㓟ࠊ࢜ࣞࣥ㓟࡛࠶ࡿ㸦Fig. 1㸧ࠋ
12 / 106 F Figure 1 ௦⾲ⓗ࡞⬡⫫㓟ࡢᵓ㐀㸦ref. 3 ࡼࡾ㌿㍕㸧 㣬⤖ྜᩘࡀቑ࠼ࡿ⛬ࠊᛂᛶࡢ㧗࠸࣓ࢳࣞࣥᇶࡀቑ࠼ࡿศᏊࡢᒅ᭤ࡀ ᙉࡃ࡞ࡿᵝᏊࡀ♧ࡉࢀ࡚࠸ࡿ 㣬 ⬡ ⫫ 㓟 ୍ ౯ 㣬 ⬡ ⫫ 㓟 ከ ౯ 㣬 ⬡ ⫫ 㓟
13 / 106 㸯㸫㸯㸫㸲㸬ᚲ㡲⬡⫫㓟 [2-15] ᚲ㡲⬡⫫㓟ࡣࠊ⏕యࡢ⥔ᣢᚲせ࡛࠶ࡿࡶ㛵ࢃࡽࡎ⏕య࡛ࡣྜᡂ ࡉࢀ࡞࠸ࡓࡵ㣗㣵ࡽᦤྲྀࡍࡿᚲせࡀ࠶ࡿ⬡⫫㓟࡛࠶ࡿࠋ ࣄࢺࡢሙྜࡣᗈ⩏࡛ࡣࢻࢥࢧ࣊࢟ࢧ࢚ࣥ㓟㸦DHA㸧ࠊ࢚ࢥࢧ࣌ࣥ ࢱ࢚ࣥ㓟㸦EPA㸧ࡸ α ࣜࣀࣞࣥ㓟㸦C18:3㸧࡞ࡢ n-3 ⣔⬡⫫㓟 ࣛ࢟ࢻࣥ㓟ࡸࣜࣀ࣮ࣝ㓟㸦C18:2㸧࡞ࡢ n-6 ⣔⬡⫫㓟ࡀᣲࡆࡽࢀࡿࠋ ణࡋࠊDHA ࡸ EPA ࡣ α ࣜࣀࣞࣥ㓟ࠊࣛ࢟ࢻࣥ㓟ࡣࣜࣀ࣮ࣝ㓟ࡽ ⏕ྜᡂࡉࢀᚓࡿࡢ࡛ࠊ⊃⩏ࡢᚲ㡲⬡⫫㓟࠸࠼ࡤ α ࣜࣀࣞࣥ㓟ࣜࣀ࣮ ࣝ㓟ࢆᣦࡍࠋᚲ㡲⬡⫫㓟ࡢḞஈࡼࡿᵝࠎ࡞ᗣ㞀ᐖࡀሗ࿌ࡉࢀ࡚ ࠸ࡿࠋ ࠼ࡤ α ࣜࣀࣞࣥ㓟ࡢḞᦆࡣ㫣≧⓶⅖ࡸ⓶ⴎ⦰㛵ࡍࡿࠋ ᚲ㡲⬡⫫㓟ࡣయෆ࡛ ࢚ࢿࣝࢠ࣮ኚࡉࢀࡓࡾࠊ⤌⧊ྲྀࡾ㎸ࡲࢀࡓ ࡾࡍࡿ⪃࠼ࡽࢀ࡚࠸ࡿࠋ ࣛࢵ ࢺࢆࡗࡓᐇ㦂࡛ࡣศゎࠊฟ 78%ࠊ ྜᡂ 6% ࡀࢃࢀࠊ16% ࡀ⬡⫫ࠊ➽⫗ࠊ⓶࡞ࡢ⣽⬊⬡㉁ࡋ࡚ ✚ࡍࡿሗ࿌ࡉࢀࡓࠋࡋࡋࠊࣄࢺయෆ࠾࠸࡚ࡣࠊDHA ࡸ EPA ࡢ ྜᡂࡢཎᩱ࡞ࡿࢆ㝖ࡁࠊṧࡾࡢ㒊ศࡀࡢᵝ࡞௦ㅰࢆཷࡅࡿࡢ ࡣ㛗ᖺ᫂ࡢࡲࡲ࡛࠶ࡿࠋα ࣜࣀࣞࣥ㓟ࡀ DHA ࡢྜᡂࢃࢀࡿྜ ࡣᖺ㱋ࡼࡗ࡚ࡁࡃ␗࡞ࡿࠋ1 ࣧ᭶㱋ࡢஙඣ࡛ࡣDHAࡢ 42% ࡀ࣑ࣝ ࢡࡽᦤྲྀࡋࡓ α ࣜࣀࣞࣥ㓟⏤᮶ࡍࡿࡀࠊ3 ࣧ᭶㱋࡛ࡣ 11%ࠊ7 ࣧ ᭶㱋࡛ࡣ 7% ῶᑡࡋ࡚࠸ࡁࠊᡂே࡛ࡣ᳨ฟ㝈⏺௨ୗ㸦<1%㸧ᴟࡵ࡚ ᑡ࡞࠸ࠋᡂ㛗ࡘࢀ ࡚ DHA ࡸ EPA ࡢྜᡂ௨እࡢ௦ㅰ⤒㊰࡛ α ࣜࣀ ࣞࣥ㓟ࡀᾘ㈝ࡉࢀ࡚࠸ࡿࡢ࡛ࡣ࡞࠸᥎ ࡉࢀ࡚ࡣ࠸ࡿࡀࠊᮍࡔ ᳨ド ⮳ࡗ࡚࠸࡞࠸ࠋ
14 / 106
㸯㸫㸰㸬ẟ㧥ࡣ
[16-27]㢌⓶ࡼࡾࡶୗ㒊ࢆẟ᰿ࠊୖ㒊ࢆẟᖿ࠸࠺ࠋ 㢌⓶ࡢ⾲⓶┿⓶ࡀẟ᰿ ࢆໟࡳ㎸ࢇ࡛㝗ධࡋࡓᗏ㒊ࡢ⭾ࡽࢇࡔ㒊ศࢆẟ⌫ࡪ㸦Fig. 2㸧ࠋẟ⌫ ࡢᇶ㒊ࡣẟங㢌ࡀᏑᅾࡋࠊẟ⣽⾑⟶ࡽᰤ㣴ࢆྲྀࡾ㎸ࢇࡔ ẟங㢌ෆࡢ ẟẕ⣽⬊ࡀ⣽⬊ศࢆ⧞ࡾ㏉ࡋ࡚ቑṪࠊゅ ࡍࡿࠋࡑ࠺ࡋ࡚ᡂ㛗ࡋࡓẟ 㧥ࡀ㢌⓶እᢲࡋฟࡉࢀࡓ㒊ศࡀẟᖿ࡛ࠊ ᪥ᖖ┠ࡋ࡚࠸ࡿẟ㧥ࡢ㒊ศ ࡛࠶ࡿࠋ ẟ㧥ࡣ┤ᚄ 40㹼100 μm ⛬ᗘࡢ⧄⥔࡛࠶ࡿࠋ᪥ᮏேẟࡢሙྜࠊᮏᩘࡣ ⣙ 10㹼15 ᮏࠊ⏕ẟᐦᗘ㸦༢㠃✚࠶ࡓࡾࡢᮏᩘ㸧ࡣ⣙ 200 ᮏ/cm2ࠊ ᡂ㛗㏿ᗘࡣ⣙ 1 cm/᭶࡛࠶ࡿࠋᑑࡣከࡃࡢሙྜ 5 ᖺ⛬ᗘࡔࡀࠊ⛥㛗 ࡃఙࡧ⥆ࡅࡿሙྜࡶ࠶ࡾࠊᩘ࣓࣮ࢺࣝ㐩ࡋࡓࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ F Figure 22 ẟ㧥ࡢ࡞ࡾࡓࡕ㸦ref. 17 ࡼࡾ㌿㍕㸧
15 / 106 ࡇ ࢀ ࡽ ࡢ ≉ ᛶ ࡣ ே ✀ ࡼ ࡗ ࡚ ᵝ ࠎ ࡛ ࠶ ࡿ ࠋ ࠼ ࡤ ⏕ ẟ ᐦ ᗘ ࡣ Caucasian ࡀ AsianࠊAfrican ࡼࡾࡶ 2㹼3 ከ࠸ࠋ୍᪉ᡂ㛗㏿ᗘ ࡣ Asian ࡀ୍␒᪩ࡃࠊḟ࠸࡛ CaucasianࠊAfrican ࡢ㡰ሗ࿌ࡉࢀ࡚ ࠸ࡿࠋ ┤ᚄᶓ᩿㠃ᙧ≧ࡣ≉ே✀ⓗ࡞≉ᚩࡀ᫂ࡽ࡛࠶ࡿࠋAsian ẟࡣ᭱ ࡶኴࡃ࡚ᶓ᩿㠃ࡀẚ㍑ⓗ┿㏆࠸ࡀࠊCaucasian ẟࡣ⣽ࡃ࡚ᴃ㏆ ࡃࠊAfrican ẟࡢኴࡉࡣ୰㛫࡛᩿㠃ࡣ୕ゅᙧࠊ㤿㋟ᙧ࡞㠀ᖖከᵝ࡞ ᙧ≧ࢆ♧ࡍࠋ௨ୗ௦⾲ⓗ࡞ᶓ᩿㠃ࡢගᏛ㢧ᚤ㙾┿ࢆ♧ࡋࡓ㸦Fig. 3㸧ࠋ
Asian hair Caucasian hair African hair
F
Figure 33 ẟ㧥ᶓ᩿㠃ࡢගᏛ㢧ᚤ㙾┿ 㸦Asian ẟࠊCaucasian ẟ
16 / 106 㸯㸫㸰㸫㸯㸬⤌⧊ [16-19, 28-41] ẟ㧥ࢆᵓᡂࡍࡿᚤ⣽ᵓ㐀ࡢ㉮ᰝᆺ㢧ᚤ㙾㸦SEM㸧ࠊ㏱㐣ᆺ㢧ᚤ㙾㸦TEM㸧 ⏬ീࢆ Figure 4㹼6 ♧ࡍࠋ ẟ㧥 ࡢ ⾲ 㠃 ࡣ㫣 ≧ࡢ ࢟ࣗ ࣮ࢸ ࢡࣝ ࡀ ⣙ 7 ᒙ✚ᒙࡋࡓ࣮࢟ࣗࢸࢡ ࣝᒙ࡛そࢃࢀ࡚࠸ࡿ㸦Fig. 4, 5㸧ࠋẟ㧥ࡢ␗᪉ᛶ㸦㡰ẟࠊ㏫ẟ᪉ྥࡀ࠶ࡿ㸧 ࡣ ࡇ ࡢ ✚ ᒙ ᵓ 㐀 ᅉ ࡿ ࡶ ࡢ ࡛ ࠶ ࡿ ࠋ ࢟ ࣗ ࣮ ࢸ ࢡ ࣝ ࡣ ẟ 㧥 ࡢ య ✚ ࡢ ⣙ 15% ࢆ༨ࡵࡿࠋᗣ࡞࣮࢟ࣗࢸࢡࣝࡣࡽ࡞㍯㒌ࠊつ๎ⓗ㓄ิ Ỉⓗ⾲㠃ࢆ᭷ࡋࠊⰋዲ࡞ᡭゐࡾࠊẟὶࢀࠊࢶࣖ➼ᐤࡋ࡚࠸ࡿࠋ ࣮࢟ࣗࢸࢡࣝ⣽⬊ࡣ A ᒙࠊ࢚࢟ࢯ࣮࢟ࣗࢸࢡࣝࡑࡋ࡚࢚ࣥࢻ࢟ࣗ ࣮ࢸࢡࣝࡢᚤ⣽ᵓ㐀ࡼࡾ࡞ࡿ 㸦Fig. 6㸧ࠋྛࠎࡀྵ᭷ࡍࡿࢩࢫࢳࣥࡢ㔞 ࡣ᫂ࡽ࡞ᕪࡀ࠶ࡾࠊA ᒙ㸦>30%㸧ࠊ࢚࢟ࢯ࣮࢟ࣗࢸࢡࣝ㸦⣙ 15%㸧ࠊ ࢚ࣥࢻ࣮࢟ࣗࢸࢡࣝ㸦⣙ 3%㸧ࡢ㡰ከ࠸ࠋࢩࢫࢳࣥࡢࢪࢫࣝࣇࢻ⤖ ྜࡣࢱࣥࣃࢡࡢᵓ㐀ࡢሀ∼ᐤࡋࠊࡑࡢྵ᭷㔞ࡀ᭱ࡶᑡ࡞࠸࢚ࣥࢻ ࣮࢟ࣗࢸࢡࣝࡣ࣮࢟ࣗࢸࢡࣝ⣽⬊୰࡛᭱ࡶ⬤࠸ᵓ㐀࡛࠶ࡿࠋ ࣮࢟ࣗࢸࢡࣝࡢෆഃࡣࢥࣝࢸࢵࢡࢫࡀᏑᅾࡍࡿ㸦Fig. 4, 5㸧ࠋࡇࢀ ࡣ⣽㛗࠸ᙧ≧ࡢࢥࣝࢸࢵࢡࢫ⣽⬊ཬࡧࢥࣝࢸࢵࢡࢫ⣽⬊㛫㉁ࡢ㞟ྜ యࡽ࡞ࡿ」㞧࡞ᵓ㐀ࡢ⤌⧊࡛࠶ࡿࠋẟ㧥ࡢయ✚ࡢ⣙ 82% ࢆ༨ࡵࠊẟ 㧥యࡢᙉᗘࢆᢸࡗ࡚࠸ࡿࠋ ẟ㧥ࡢ୰ᚰ㒊ࡣ࣓ࢹࣗࣛࡀ࠶ࡿ㸦Fig. 4㸧ࠋࡇࢀࡣࢱࣥࣃࢡ㉁ ⬡㉁ࡽ࡞ࡿ✵Ὕࡢከ࠸ᵓ㐀࡛ࠊẟ㧥య✚ࡢ⣙ 3% ࢆ༨ࡵࡿ㹿ࡋࡋ࢟ ࣮ࣗࢸࢡࣝࡸࢥࣝࢸࢵࢡࢫࡣ␗࡞ࡾࠊ࣓ࢹࣗࣛࡢᏑᅾࡋ࡞࠸ẟ㧥ࡀ ࠶ࡿࡋࠊ1 ᮏࡢẟ㧥࡛ࡶᏑᅾࡍࡿ⟠ᡤᏑᅾࡋ࡞࠸⟠ᡤࡀ࠶ࡿࠋയࢇ ࡔẟ㧥ࡢ࣓ࢹࣗࣛࡣࡁ࠸࠸࠺ഴྥࡀ࠶ࡾࠊ≀ᛶࡸእほࡢຎࡢཎᅉ ࡢ୍ࡘ⪃࠼ࡽࢀ࡚࠸ࡿࠋኴ࠸㧥ࡣඖࠎ࣓ࢹࣗࣛࡢయ✚⋡ࡀ㧗ࡃࠊ⣽࠸
17 / 106 㧥࡛ࡣప࠸ഴྥࡀ࠶ࡿࡼࡾࠊᑡ࡞࠸ࢱࣥࣃࢡ㉁࡛࠶ࡿ⛬ᗘࡢኴࡉࡢయ ẟࢆᩘከࡃసࡿࡓࡵࡢᏑᅾ࡛࠶ࡿࠊ✵Ẽࢆᢪ࠼㎸ࢇ࡛ಖ ຠᯝࢆᣢ ࡘᙺࢆࡍࡿ࡞⪃࠼ࡽࢀ࡚࠸ࡿࠋ ࣮࢟ࣗࢸࢡࣝ㸫࣮࢟ࣗࢸࢡࣝ⣽⬊㛫ࠊ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵ ࢡ ࢫ 㛫 ࡑ ࡋ ࡚ ࢥ ࣝ ࢸ ࢵ ࢡ ࢫ 㸫 ࢥ ࣝ ࢸ ࢵ ࢡ ࢫ ⣽ ⬊ 㛫 ࡣ ⣽ ⬊ ⭷ 」 ྜ య 㸦Cell membrane complexࠊCMC ␎ࡉࢀࡿ㸧ࡀᏑᅾࡍࡿ㸦Fig. 6㸧ࠋ ᖜ 25 nm ⛬ࡢᖏ≧ࡢ⤌⧊࡛ࠊ୰ኸࢱࣥࣃࢡ㉁ࡽᡂࡿ δ ᒙࠊࡑࡢ୧ ഃ⬡㉁ᒙ࡛࠶ࡿ β ᒙ 2 ࡘࡀ⨨ࡍࡿ୕ᒙᵓ㐀ࢆࡿࠋCMC ࡣእ㒊 ࡽࡢ≀㉁ࡢ࡞ᾐ㏱⤒㊰࡛࠶ࡿࠋ ࣮࢟ࣗࢸࢡࣝ 㛫 CMC ࡢ β ᒙࡢෆࠊෆഃࡢ࣮࢟ࣗࢸࢡࣝ᥋ࡋ ࡓ᪉ࢆ outer β ᒙࡪࠋᗣ࡞ẟ㧥⾲㠃ࡣࡇࡢ outer β ᒙ࡛そࢃࢀ࡚ ࠸ࡿࠋศᒱ㙐⬡⫫㓟 18 ࣓ࢳ࢚ࣝࢥࢧࣥ㓟㸦18-MEA㸧ࡣࡇࡢ outer β ᒙ ೫ᅾࡋ࡚ࢱࣥࣃࢡ㉁ࢳ࢚࢜ࢫࢸࣝ⤖ྜ࡛⤖ྜࡋࠊẟ㧥⾲㠃ࢆỈᛶ ಖࡕࠊឤゐࡢࡽࡉࡸẟὶࢀࡢⰋࡉᐤࡋ࡚࠸ࡿࠋ ࣓ࣛࣀࢯ࣮࣒㸦࣓ࣛࢽࣥ㢛⢏㸧㸦Fig. 5㸧ࡣࢥࣝࢸࢵࢡࢫᏑᅾࡋࠊ ࣮࢟ࣗࢸࢡࣝࡣ⛥ࡋぢࡽࢀ࡞࠸ ࠋAsian ࡢ㯮㧥ྵࡲࢀࡿ࣓ࣛ ࣀࢯ࣮࣒ࡣ⡿⢏≧ࡢᙧ≧ࢆࡋ࡚࠾ࡾࠊ ࢧࢬࡣ㛗ᚄ 0.8 μmࠊ▷ᚄ 0.4 μm ⛬࡛ࠊ㯮㏆࠸⃰ⲔⰍ࡛࠶ࡿࠋ⧄⥔≧ࡢࢱࣥࣃࢡ㉁ࡀᵓ㐀ࡢ㦵᱁ࢆ ᙧᡂࡋࠊࡑࢀ㧗⃰ᗘࡢ࣓ࣛࢽࣥⰍ⣲ࡀ⤖ྜࡋࡓࡶࡢ࡛ࠊ⬡㉁㔜⭷࡛ ᅖࡲࢀ࡚࠸ࡿࠋ࣓ࣛࣀࢯ࣮࣒ࡣẟẕ⣽⬊Ꮡᅾࡍࡿ࣓ࣛࣀࢧࢺ࡛⏕ྜ ᡂࡉࢀࠊࡑࡢᚋゅ㡿ᇦ⛣ືࡋ࡚࠸ࡃࡀࠊࡑࡢ⏕ྜᡂ㹼⛣ືࡢ㐣⛬ ⬡㉁ࡀ㛵ࡍࡿ᥎ ࡉࢀ࡚࠸ࡿࠋ
18 / 106 F Figuure 44 ᩳࡵ࢝ࢵࢺࡋࡓẟ㧥ࡢSEM ⏬ീ ࢟ ࣗ ࣮ ࢸ ࢡ ࣝ F Figure 55 ẟ㧥⦪᩿㠃 TEM ⏬ീ ࢥࣝࢸࢵࢡࢫෆࡢ㯮࠸㢛⢏ࡣ࣓ࣛࣀࢯ࣮࣒㸦࣓ࣛࢽࣥ㢛⢏㸧 ࢥ ࣝ ࢸ ࢵ ࢡ ࢫ 10μm ࢟ ࣗ ࣮ ࢸ ࢡ ࣝ ࢥ ࣝ ࢸ ࢵ ࢡ ࢫ ࣓ ࢹ ࣗ ࣛ
19 / 106 F Figure 66 ẟ㧥ᶓ᩿㠃ࡢ࣮࢟ࣗࢸࢡࣝ㒊ศࡢ TEM ⏬ീ ࢚ ࣥ ࢻ࢟ ࣗ ࣮ࢸ ࢡ ࣝ ࢚ ࢟ ࢯ࢟ ࣗ ࣮ࢸ ࢡ ࣝ A ᒙ CMC inner β ᒙ δ ᒙ outer β ᒙ
20 / 106 㸯㸫㸰㸫㸰㸬ᵓᡂᡂศ [16-19, 42] ẟ㧥ࢆᵓᡂࡍࡿᡂศࡢ㒊ศࡀࢱࣥࣃࢡ㉁࡛ࠊ65㹼95 wt% ࢆ༨ࡵࡿࠋ ࢱࣥࣃࢡ㉁ḟ࠸࡛Ỉศ㸦⣙ 10 wt%㸧ࠊ⬡㉁㸦1㹼9 wt%㸧ࠊࡑࡋ࡚ᚤ㔞 ᡂศ㸦<1 wt%㸧ࡢ↓ᶵ㉁㸦CaࠊMgࠊAlࠊSiࠊNaࠊKࠊZnࠊCu ➼㸧ࡀ ྵࡲࢀࡿࠋ↓ᶵ㉁ࡣờࠊ㣗㣵ࠊẼࡸᅵተࠊỈࡽ ẟ㧥⛣⾜ࡋࡓ ࡶࡢ⪃࠼ࡽࢀࡿࠋ↓ᶵ㉁ࡢෆࡢ࠸ࡃࡘࡣࠊࡑࡢከᐻࡀᵝࠎ࡞Ẽࡢ Ⓨᐦ᥋㛵ࢃࡗ࡚࠸ࡿࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ
21 / 106
㸯㸫㸱㸬ẟ㧥ࡢ⬡㉁
[16, 43-52] ẟ㧥࠾࠸࡚⬡㉁ࡣ ࢱࣥࣃࢡ㉁Ỉḟࡄせ࡞ᵓᡂᡂศ࡛࠶ࡿࠋ⓶ ⬡ࡸ࣊ࢣ〇ရ࡞⏤᮶ࡍࡿእᅉᛶ⬡㉁ࡋ࡚ࡣ ࣝ࢝ࣥࠊࢫࢡ ࣞࣥࠊ࣡ࢵࢡࢫ࢚ࢫࢸࣝࠊ୰ᛶ⬡⫫ࠊ㧗⣭ࣝࢥ࣮ࣝࠊ⬡⫫㓟➼ࠊࡑࡋ ࡚ẟ㧥⮬య⏤᮶ࡍࡿෆᅉᛶ⬡㉁ࡋ࡚ࡣ⬡⫫㓟ࠊ ࢥࣞࢫࢸ࣮ࣟࣝࠊࢭ ࣑ࣛࢻࠊࢥࣞࢫࢸ࣮࢚ࣟࣝࢫࢸࣝ➼ࡀ࡞≀ࡋ࡚ᣲࡆࡽࢀࡿࠋ22 / 106 㸯㸫㸱㸫㸯㸬ศᕸ [49-52] ෆᅉᛶ⬡㉁ࡣ࣮࢟ࣗࢸࢡࣝࡸࢥࣝࢸࢵࢡࢫࡢ⣽⬊㛫 CMC ࡢ β ᒙࠊ ࣓ࣛࣀࢯ࣮࣒⤖ྜ⭷ࡸ࣓ࢹࣗࣛẚ㍑ⓗከ㔞Ꮡᅾࡋ࡚࠸ࡿࠋ ẟ㧥ࡢᡂ㛗㐣⛬కࡗ࡚⬡㉁ࡢศᕸࡣኚࡍࡿࠋLee ࡽࡣẟໟࠊෆẟ ᰿㠧ࠊẟᖿࡢ㡰ࠊゅ㐍⾜ᗘࡢึᮇࡽᚋᮇࡅ࡚ࢫࢸ࣮ࢪࡈ ⬡㉁ࢆ ᐃࡋࠊ⬡㉁ࡢྜࢆ௨ୗࡢᵝሗ࿌ࡋࡓࠋ ẟໟ㸸⬡⫫㓟 > ࣇࢺࢫࣇࣥࢦࢩࣥ > ࢭ࣑ࣛࢻ > ࢥࣞࢫࢸ࣮ࣟࣝ > ◲㓟ࢥࣞࢫࢸ࣮ࣟࣝ ෆẟ᰿㠧㸸⬡⫫㓟 > ࣇࢺࢫࣇࣥࢦࢩࣥ > ࢭ࣑ࣛࢻ > ࢥࣞࢫࢸ࣮ࣟࣝ > ࢜ࣞࣥ㓟ࢥࣞࢫࢸ࣮ࣟࣝ ẟᖿ㸸ࣇࢺࢫࣇࣥࢦࢩࣥ > ⬡⫫㓟 > ࢭ࣑ࣛࢻ > ࢥࣞࢫࢸ࣮ࣟࣝ > ◲㓟ࢥࣞࢫࢸ࣮ࣟࣝ
23 / 106 㸯㸫㸱㸫㸰㸬⢾⬡㉁ ⨺ẟࡢෆ㒊ࡣ㔞ࡢ⢾⬡㉁⢾ࢭ࣑ࣛࢻࡀྵࡲࢀࡿࡀሗ࿌ࡉࢀ࡚ ࠸ࡿ [53]ࠋྠᵝࣄࢺẟ㧥ࡶࠊᚤ㔞ࡢ⢾⬡㉁ࡀྵࡲࢀࡿ⪃࠼ࡽࢀ࡚ ࠸ࡿ [54-56]ࠋ࠼ࡤࠊ⾑ᾮᆺ A ᆺࡢẟ㧥ᢳฟ≀ࡣ N -ࢭࢳࣝ࢞ࣛ ࢡࢺࢧ࣑ࣥ㸦GalNAc㸧ࡢ⤖ྜࡋࡓ⾑ᾮᆺ A-άᛶ⢾⬡㉁ࡀྵࡲࢀࡿࡀ ♧၀ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊN -ࢭࢳࣝࢢࣝࢥࢧ࣑ࣥ㸦GlcNAc㸧ࡲࡓࡣ GalNAc ࢆ㦵᱁ࡢ୍㒊ࡋ࡚ྵࡴࢫࢸࣜࣝࢢࣜࢥࢩࢻ㸦SG㸧ᵝ⬡㉁ࡢᏑ ᅾࡀ 2011 ᖺሗ࿌ࡉࢀ࡚࠸ࡿ [57]ࠋ
24 / 106 㸯㸫㸱㸫㸱㸬ᶵ⬟ ẟ㧥ࡢ⬡㉁ࡣᚤ⣽ᵓ㐀ࡢ⬡㉁⭷ᙧᡂࠊẟ㧥⾲㠃ཬࡧ⤌⧊㛫ࡢ₶ࠊ ⤌⧊ᵓ⠏ᡂศࡢ⏕ྜᡂࡢሙࡢ㍺㏦ࠊゅᚋࡢ⤌⧊ࡢ≀ᛶࡢไᚚ࡞ ࠾࠸࡚ᵝࠎ࡞㔜せ࡞ᙺࢆᯝࡓࡋ࡚࠸ࡿࠋ ࠼ࡤࠊᖖẟ㧥⾲㠃Ꮡᅾࡍࡿ 18-MEA ࡣ⾲㠃ࢆỈⓗಖࡕࠊ 㧥ࡽ࡞ឤゐࢆ࠼࡚࠸ࡿࠋ᭦ࠊࡑࡢࣂ࣮ࣝ࢟࡞ᵓ㐀ࡀ࣮࢟ࣗࢸ ࢡࣝ⣽⬊㛫 CMC ࡢ packing ࢆ⦆ࡵ࡚ࠊ࣮࢟ࣗࢸࢡࣝ㛫ࡢࡾᛶ ࢆ㧗ࡵ่࡚⃭ࡼࡿ㈇ⲴࢆపୗࡉࡏࡿຠᯝࢆⓎࡍࡿ [33, 37-40]ࠋ 18-MEA ࢆᣢࡓ࡞࠸ඛኳⓗ࡞Ẽ࡛࠶ࡿ࣓࣮ࣉࣝࢩࣟࢵࣉᒀᝈ⪅ࡢ ẟ㧥࡛ࡣࠊ࣮࢟ࣗࢸࢡࣝࡢᵓ㐀ⓗ࡞Ḟᦆࡀ ࠎࡋ࡚ほᐹࡉࢀࡿ [38]ࠋ ẟ㧥ࡢᚲ㡲⬡㉁㔞 UV ↷ᑕࡼࡿࢲ࣓࣮ࢪࢆ AsianࠊEuropeanࠊ African ࡢ㸱ே✀࡛ẚ㍑ࡋࡓ◊✲ࡢ⤖ᯝࠊᚲ㡲⬡㉁㔞ࡢከ࠸ Asian ẟࡀ ᭱ࡶ UV ࢲ࣓࣮ࢪࡀᑠࡉࡗࡓࡼࡾࠊᚲ㡲⬡㉁ࡣ UV ࡽ㧥ࢆ㜵 ᚚࡍࡿാࡁࡀ࠶ࡿ⪃ᐹࡉࢀࡓ [58]ࠋࡲࡓࠊX ⥺ゎᯒࡼࡾAfricanẟ ࡛ࡣෆᅾ⬡㉁ࡢᏑᅾࡼࡗ࡚ࢣࣛࢳࣥࢱࣥࣃࢡࡢ packing 㓄ิࡀᦆ࡞ ࢃࢀ࡚࠸ࡿࡀぢฟࡉࢀࠊ㧗⃰ᗘࡢ⬡㉁ࡀࢣࣛࢳࣥ㔞యࡢ㛫ධࡾ㎸ ࢇ࡛ᵓ㐀ࢆኚࡉࡏࡓ⪃࠼ࡽࢀ࡚࠸ࡿ [59]ࠋ ⏕ྜᡂ㐣⛬ㄪ⠇ᶵ⬟ࡘ࠸࡚ࡶሗ࿌ࡉࢀ࡚࠸ࡿ [60, 61]ࠋ࣐࢘ࢫ࡛ࡣ ⬡㉁௦ㅰࡢ㑇ఏⓗᝈࡀ⅖ࡸ␗ᖖᡂ㛗ẟ࡞ࢆ㉳ࡇࡍᩘከࡃࡢࡀሗ ࿌ࡉࢀࡓࠋࣄࢺ࡛ࡣࠊங࢞ࣥᝈ⪅ࡢẟ㧥ぢࡽࢀࡓࢣࣛࢳࣥࢱࣥࣃࢡ β ࢩ࣮ࢺᵓ㐀⬡㉁㔞ࡢ␗ᖖࡀ࢞ࣥษ㝖ᚋࡣṇᖖᖐࡋࡓࡼࡾࠊங ࢞ࣥࡢࢩࢢࢼࣝఏ㐩ศᏊࡼࡾẟໟෆࡢ⬡㉁⏕ྜᡂ㐣⛬ኚࡀ⏕ࡌࡓ ࡶࡢ⪃࠼ࡽࢀࡓࠋ
25 / 106 㸯㸫㸱㸫㸲㸬ᚲ㡲⬡⫫㓟௦ㅰࡢሙࡋ࡚ࡢẟ㧥 [62, 63] 㣗ࡽᦤྲྀࡉࢀࡓᚲ㡲⬡⫫㓟ࡣయෆ࡛௦ㅰࡉࢀࡿࠋẟ㧥ࡣࡑࡢ௦ㅰ ࡢሙࡢ୍ࡘ࡛࠶ࡿࡶࡋࢀ࡞࠸ ࠋ Fu Sinclair ࡣ 14C ࡛ 1 ࢆࣛ࣋ࣝࡋࡓ α ࣜࣀࣞࣥ㓟㸦ALA㸧 ධࡾࡢ㣵࡛㣫⫱ࡋࡓ ࣔࣝࣔࢵࢺࡢྛ⤌⧊ࡢ ALA 㔞ࢆ ᐃࡋࡓࠋࡑࡢ⤖ ᯝࠊࣛ࣋ࣝ ALA ࡢ 46% ௨ୖࡀ⓶యẟࡢ⬡㉁⛣⾜ࡋࠊࡾࢃ ࡅ㢌ẟཬࡧ㢌⓶୰ከࡃᏑᅾࡍࡿࡀࢃࡗࡓࠋ㢌㒊࡛ࡣࠊ㠀ࣛ࣋ࣝ ≀ࡶྵࡵࡓ⤌⧊࠶ࡓࡾࡢ⥲ ALA 㔞ࡣࡢ⤌⧊㸦⫢⮚ࡸ⮅⮚࡞㸧ẚ ࡚ࡎࡗᑡ࡞࠸ࡶ㛵ࢃࡽࡎ ࠊẚᨺᑕ⬟ࡀᴟࡵ࡚㧗ࡗࡓࡼࡾࠊᦤ ྲྀࡉࢀࡓࣛ࣋ࣝ ALA ࡀ௦ㅰࡉࢀࡿ๓㏿ࡸ㢌㒊⛣⾜ࡋࡓ࠸ ࠺ࡀࢃࡿࠋ᭦ࠊALA ࡢ DHA ࡢኚ⋡ࡀ㠀ᖖᑠࡉ࠸࠸࠺ ࡶぢฟࡉࢀࡓࠋALA ࡢࣄࢺయෆືែࡣࢇࢃࡗ࡚࠸࡞࠸ࡀࠊࡇ ࡢࣔࣝࣔࢵࢺࡢ◊✲⤖ᯝࡀࣄࢺ ࡶᙜ࡚ࡣࡲࡿࡍࢀࡤࠊALA ࡣࣄࢺࡢ ẟ㧥࣭㢌⓶࠾࠸࡚ఱ≉ู࡞௦ㅰ⤒㊰ࢆ⤒࡚ఱࡽࡢ⏕⌮Ꮫⓗᙺࢆ ᯝࡓࡋ࡚࠸ࡿࡢ࡛ࡣ࡞࠸ᮇᚅࡉࢀࡿࠋ
26 / 106
㸯㸫㸲㸬┠ⓗ
⬡㉁ࡢẟ㧥ᚤ⣽ᵓ㐀࡛ࣞ࣋ࣝࡢ ศᕸᵓ㐀ࢆ᫂ࡽࡋࠊẟ㧥ෆᅾ⬡ ㉁ࡢᙺࢆ⪃ᐹࡍࡿࠋ᭦ࠊ㛗ᖺரࡾࣄࢺయෆືែࡀㅦ࡛࠶ࡗࡓᚲ㡲 ⬡⫫㓟ࡢ௦ㅰࡢሙࡋ࡚⓶࣭ẟ㧥⣔ࢆᤊ࠼ࠊ௦ㅰ⤒㊰ࡸᶵ⬟ࡘ࠸࡚ ㄽࡌࡿࠋ27 / 106
㸯㸫㸳㸬᪉ἲ
ᮏㄽ࡛⏝ࡍࡿ≀㉁ࠊ ᐃᡭἲࡢ␎ྡࢆ௨ୗิグࡋࡓࠋ ALA: Alpha-linolenic acid
ATR: Attenuated total reflection CMC: Cell membrane complex DMOX: 4,4-dimethyloxazoline
ESI-MS: Electro-spray ionization mass spectrometry ESG: Ester sterylglycoside
FTIR: Fourier-transform infrared GalNAc: N-Acetyl galactosamine
GCMS: Gas chromatography-mass spectrometry GlcNAc: N-Acetyl glucosamine
HPLC: High performance liquid chromatography MS: Mass spectrometry
MS/MS: Tandem mass spectrometry PUFA: Polyunsaturated fatty acid SEM: Scanning electron microscope SG: Sterylglycoside
SGL: Sterylglycoside-like lipid
TEM: Transmission electron microscope
ToF-SIMS: Time-of-flight-secondary ion mass spectrometry UPLC: Ultra high performance liquid chromatography
28 / 106
ᮏ◊✲࡛ࡣẟ㧥ࡢ⾲㠃㸦࣮࢟ࣗࢸࢡࣝ㸧ࠊෆ㒊㸦ࢥࣝࢸࢵࢡࢫࠊ࣓ࢹ ࣗࣛࠊ࣓ࣛࢽࣥ㢛⢏㸧ࠊ࣮࢟ࣗࢸࢡࣝࢥࣝࢸࢵࢡࢫࡢ⏺㠃ࡑࡋ࡚ẟ⌫
ࡑࢀࡒࢀࡢ㡿ᇦ࡛ FTIR ࡸ MS㸦ToF-SIMS, GCMS, ESI-MS㸧࡞
ࡢᶵჾศᯒࡼࡗ࡚ ⬡㉁ࡑࡢ௦ㅰ≀ࢆ᳨ฟࡋᵓ㐀ྠᐃࢆ⾜ࡗࡓࠋ 㹙ẟ㧥ヨᩱ㹛 10㹼30 ௦ࡢ᪥ᮏேዪᛶࡢẟ㧥ࢆ㢌⓶ࡽ 1 mm ௨ෆࡢ⨨࡛࢝ࢵ ࢺࡋࠊᏛฎ⌮ᒚṔࡢ↓࠸㒊ศࢆ ᐃ⏝࠸ࡓࠋࡲࡓࠊ⮬↛⬺ẟࡋࡓẟ 㧥ࡢẟ⌫㒊ศࡶ⏝ࡋࡓࠋẟ㧥ᥦ౪⪅ࡣ◊✲ࡢ┠ⓗࠊヨᩱཬࡧᐇ㦂 ࢹ࣮ ࢱࡢྲྀࡾᢅ࠸➼ࡘ࠸࡚⌮ᇶ‽๎ࡗࡓヲ⣽࡞ㄝ᫂ࢆཷࡅࠊྠពࡢୖ ࡛ᥦ౪ࢆ⾜ࡗࡓࠋ ᐇ㦂ඛ❧ࡕࠊᚲせᛂࡌ࡚௨ୗࡢձࠊղ࠸ࡎࢀࡢ᪉ἲ࡛ẟ㧥ヨᩱ ࢆὙίࡋࠊ⾲㠃ࡢ⓶⬡ࠊ㠀ඹ᭷⤖ྜ⬡㉁ࡸእᅉᛶࡢᏛ≀㉁ࢆ㝖࠸ࡓࠋ
ձ⏺㠃άᛶࡢỈ⁐ᾮ㸦15 wt% Sodium polyoxyethylene lauryl ether
sulfate aq. ࢆࣜࣥ㓟࡛ pH 7 ㄪ⠇㸧࡛ 3 ᅇὙίᚋࠊ᭦ Ethanolࠊ Hexane ࡛Ὑί ղỈὙᚋ Ethanol ࡲࡓࡣ Acetone 2㹼3 ᪥ᾐₕ 㹙ヨ⸆㹛 CHCl3ࠊMethanol ࡣ≉⣭ရࢆ㛵ᮾᏛࡽ㉎ධࡋ࡚⏝࠸ࡓࠋ⬡⫫㓟 ࡢ࣓ࢳ࢚ࣝࢫࢸࣝ⏝ࡋࡓ HCl-Methanol㸦5-10%㸧ᾮࡣᮾிᡂࠊ ⬡⫫㓟ࡢ DMOX ㄏᑟయ⏝ࡋࡓ 2-Amino-2-methyl-1-propanol 㸦Ӎ95%㸧ࡣ Sigma-Aldrich㸦USA㸧ࡽ㉎ධࡋࡓࠋ
29 / 106 ࣓ࣛࣀࢯ࣮࣒༢㞳⏝࠸ࡓࣃࣃࣥࣜࣥ㓟⦆⾪ᾮ㸦pH 6.86㸧ࡣ ග⣧⸆ࠊࢪࢳ࢚࢜ࣜࢺࣜࢺ࣮ࣝ㸦Ӎ99%㸧ࡣ Sigma-Aldrich ࡽ㉎ධࡋ ࡓࠋ 㹙⦪ศẟస〇㹛 ẟ㧥ෆ㒊ࡢ ᐃࡢⅭࠊගᏛ㢧ᚤ㙾ほᐹୗ࡛࣑ࢽ㕹㸦Mini-plane, ᪥ ᮏ㸧ࢆ⏝࠸࡚⦪ศẟࢆస〇ࡋࡓࠋ 㹙࣮࢟ࣗࢸࢡࣝ㞳ẟస〇㹛 Ꮫฎ⌮ࡼࡿ⬡㉁ኚᛶࢆ㑊ࡅࡿⅭࠊḟࡢ 2 ㏻ࡾࡢ᪉ἲ࡛ᶵᲔຊ ࡼࡗ࡚࣮࢟ࣗࢸࢡࣝࢆ㝖࠸ࡓࠋ ձࣁࣈࣛࢩἲ㸸࣮࢟ࣗࢸࢡࣝࢆࣜࣇࢺࢵࣉࡉࡏ࡚ࡀࢀ᫆ࡃࡍࡿⅭ 50 mm ࡢẟ㧥ࢆᘬࡗᙇࡾᅽ⦰ヨ㦂ᶵ TG-500N㸦࣑ࢿ࣋㸧ࢆ⏝࠸࡚ ᘏఙࡋࡓࠋᘏఙࡣ 20°Cࠊ20% ┦ᑐ‵ᗘࡢ᮲௳ୗ࡛⾜࠸ࠊẟ㧥ࡢ≧ែ ᛂࡌ࡚ษࢀ࡞࠸ࡼ࠺ᘏఙࣞ࣋ࣝࢆㄪ⠇㸦᭱ 135%㸧ࡋࡓࠋࡑࡢᚋẟ 㧥ࢆྲྀࡾእࡋࠊᖹࡽ࡞ྎୖᅛᐃࡋ࡚ࠊẟඛࡽ᰿ඖྥࡗ࡚ ࣁࣈࣛ ࢩ GUM #191㸦ࢧࣥࢫࢱ࣮㸧࡛ᩘⓒᅇ᧿ࡗࡓࠋ㐺ᐅẟ㧥⾲㠃ࢆ࣮ࣞࢨ㢧 ᚤ㙾 VK-8700 㸦࣮࢚࢟ࣥࢫ㸧࡛ほᐹࡋࠊ࣮࢟ࣗࢸࢡࣝ㞳ࣞ࣋ࣝࡀ ୗグ TB1ࠊTB2 㐩ࡍࡿࡲ࡛ࠊ௨ୖࡢᡭ㡰ࢆ⧞ࡾ㏉ࡋࡓࠋ ࣭TB1㸦㒊ศ㞳ࣞ࣋ࣝ㸧㸸࣮࢟ࣗࢸࢡࣝᒙࡢ⣙༙ศ㸦⣙ 3㹼4 ᒙ㸧 ࡀṧᏑ ࣭TB2㸦ࡰ㞳ࣞ࣋ࣝ㸧㸸࣮࢟ࣗࢸࢡࣝ 1㹼2 ᒙࡀṧᏑࠊࢥࣝ ࢸࢵࢡࢫ⾲㠃ࡢ㟢ฟ㠃✚ࡣ 50% ௨ୗ
30 / 106 ղࣅ࣮ࢬἲ㸸୰ᚰᅇ㌿㍈ࡢࡘ࠸ࡓ┤ᚄ 130 mm ࡢࢫࢸࣥࣞࢫ〇⟄⾲ 㠃ẟ㧥ࢆࢸ࣮ࣉ࡛㈞ࡾࡘࡅࡓ㸦Fig. 7 A㸧ࠋ┤ᚄ 200 mm ࡢࢫࢸࣥࣞ ࢫ〇⟄≧ᐜჾ࣑ࣝࢼࡢࣅ࣮ࢬ㸦┤ᚄ 2 mm㸧ࢆ‶ࡓࡋࠊࡑࡇ A ࢆᕪࡋ㎸ࢇࡔࠋA ࡢᅇ㌿㍈ࢆ᧠ᢾ࣮ࣔࢱ࣮ࡢࢫ࣮࣮ࣜ࣡ࣥࣔࢱ HEIDON 600G㸦᪂ᮾ⛉Ꮫ㸧ྲྀࡾࡅ࡚ᅇ㌿ࡉࡏ㸦Fig. 7 B㸧ࠊẟ㧥ࣅ࣮ࢬࢆ ⾪✺ࡉࡏ࡚࣮࢟ࣗࢸࢡࣝࢆ๐ࡾྲྀࡗࡓࠋ㐺ᐅẟ㧥⾲㠃ࢆ࣮ࣞࢨ㢧ᚤ㙾 VK-8700 ࡛ほᐹࡋࠊ㐺ᙜ࡞ࢱ࣑ࣥࢢ࡛⾲ࢆ㏉ࡋࡓࠋ࣮࢟ࣗࢸࢡࣝ ࡀ㝖ࢀ࡚ࢥࣝࢸࢵࢡࢫ⾲㠃యࡀ㟢ฟࡍࡿࡲ࡛⥆ࡅࡓࠋࡇࢀࢆ 㞳ࣞ࣋ࣝ㸦BD㸧ࡍࡿࠋ TB1ࠊTB2ࠊBD ྛࠎࡢࣞ࣋ࣝࡘࡁẟ㧥ࢆ 5㹼10 ᮏస〇ࡋࠊ࢜ࣥ ỈࠊEthanolࠊHexane 1 ศࡎࡘᾐₕࡋ࡚㢼ࡋࡓࠋ Figure 7 ࣮࢟ࣗࢸࢡࣝ㞳᪉ἲ㸦ࣅ࣮ࢬἲ㸧 A 130 mm ࣑ࣝࢼࣅ࣮ࢬ 200 mm ẟ㧥 B ࣔ ࣮ ࢱ ࣮
31 / 106 㹙⬡㉁ᢳฟ㹛 ẟ㧥ヨᩱࢆ㐣ࡢ␃Ỉ 30 ศࠊḟ࠸࡛ CHCl3-Methanol㸦Vol ẚ 2/1㸧ᾮ 2 ᪥㛫ᾐₕࡋ࡚Ὑίᚋࠊ㢼ࠋ␃Ỉ 0.5 ml 15% KOH/Ethanol ⁐ᾮ 0.5 ml ࢆຍ࠼࡚ 60°C ࡛ 2 hr ຍ⇕ࡋࠊ㮯ࢆ⾜ ࡗࡓࠋୖΎࢆࡾࠊ10% HCl aq. 140 μl Hexane 1 ml ࢆຍ࠼࡚ 1 ศ 㛫࣎ࣝࢸࢵࢡࢫ࣑࢟ࢧ࣮࡛᧠ᢾࡋࠊᒙ࡞ࡗࡓᾮࡢୖᒙࢆ᥇ྲྀࡋࡓࠋ ṧࡾࡢᾮ᭦ Hexane 1 ml ࢆຍ࠼࡚᧠ᢾࡋࠊୖᒙࢆ᥇ྲྀࡍࡿᕤ⛬ࢆ 2 ᅇ⧞ࡾ㏉ࡋࡓࠋ3 ᅇศࡢୖᒙࢆྜࢃࡏࠊN2 ࢞ࢫ࡛ᅛࡋ࡚⬡⫫㓟ࢆᚓ ࡓࠋ 㹙⬡⫫㓟ࡢ࣓ࢳ࢚ࣝࢫࢸࣝ㹛 DMOX ㄏᑟయඛ❧ࡕࠊ⬡⫫㓟ࡢ࣓ࢳ࢚ࣝࢫࢸࣝࢆ⾜ࡗࡓ [64]ࠋ ẟ㧥ᢳฟ⬡㉁ 5% HCl-Methanol ᾮ 0.15 ml ↓Ỉ Methanol 0.35 ml ࢆຍ࠼ࠊᐦᑒࡋࡓ࢞ࣛࢫ⟶୰࡛ 100°Cࠊ4 hr ຍ⇕ࡋࡓࠋᐊ ࡲ࡛෭ ༷ࡋࡓᚋ 1 ml ࡢ Hexane ࢆຍ࠼ࠊMS ᐃࡲ࡛ -20°C ࡛ಖᏑࡋࡓࠋ MS ᐃࡣ N2 ࢞ࢫ࡛⁐፹ᅛᚋࠊ10 μl ࡢ Hexane ࢆຍ࠼࡚ヨᩱ ࡋࡓࠋ 㹙⬡⫫㓟ࡢ DMOX ㄏᑟయ㹛 ศᏊෆࡢ㣬⤖ྜࡢ⨨ࢆ▱ࡿࡓࡵ DMOX ㄏᑟయࢆ⾜ࡗࡓ [65]ࠋ࣓ࢳ࢚ࣝࢫࢸࣝࡋࡓ⬡⫫㓟ࢆ⇱ᚋࠊHexane ࡛Ὑࡗࡓ 2-Amino-2-methyl-1-propanol ᾮ㸦0.5 ml㸧ΰྜࠊN2 ୗ࡛࣎ࣝࢸࢵࢡ ࢫ࣑࢟ࢧ࣮࡛᧠ᢾࡋ ࠊ୍ᬌ 150°C࡛ຍ⇕ࡋࡓࠋᐊ ෭༷ᚋࠊ㣬 NaOHaq.㸦0.5 ml㸧࢜ࣥỈ㸦0.5 ml㸧ࢆຍ࠼࡚ΰྜࡋࠊ࣎ࣝࢸ
32 / 106 ࢵࢡࢫ࣑࢟ࢧ࣮࡛᧠ᢾࠋ᭦ 4 ml ࡢ Diethylether/Hexane㸦Vol ẚ 1/1㸧 ࢆຍ࠼࡚ 1 ศ㛫᧠ᢾᚋࠊ3000 rpm ࡛ 5 ศ㛫㐲ᚰศ㞳ࡋࡓࠋᾮࡢୖᒙ ࢆ᥇ࡗ࡚ N2 ୗ࡛ࡋࠊ-20°C࡛ಖᏑࡋࡓࠋ 㹙ESG ESG ᵝ⬡㉁ࡢຍỈศゎ㹛 ⬡㉁ࢆ 1 ml ࡢ 3M HCl ΰྜࡋ࡚ 100°C࡛ 4 hr ຍ⇕ࡋࠊ෭༷ᚋࠊ Bligh-Dyer ἲ๎ࡗ࡚⬡㉁ᒙỈ/Methanol ᒙࢆศ⏬ࡋࡓ [66]ࠋ୧ᒙ ࢆ⃰⦰ࡋࠊ-20°C࡛ಖᏑࡋࡓࠋຍỈศゎ ESG ᵝ⬡㉁ࡢぶỈᛶ⏕ᡂ≀ ᶆ‽ရࡢ GlcNAc ࢆࢭࢳࣝࡍࡿ㝿ࡣࠊ┿✵⇱ࡋࡓヨᩱࢆ THFࠊ↓Ỉ㓑㓟ࠊඹゐ፹ࡢ 4-(Dimethylamino) pyridine ΰྜࡋࠊᐊ ୗ 24 hr ᛂᚋ Sodium bicarbonate ࡛୰ࡋ࡚ࢭࢳࣝࡋࡓࢧ ࣥࣉࣝࢆᢳฟࡋࠊῶᅽ⃰⦰ࢆ⾜ࡗࡓ [67]ࠋ 㹙࣓ࣛࣀࢯ࣮࣒ࡢ༢㞳㹛 ௨ୗࡢ᪉ἲ࡛ẟ㧥ࡢࢱࣥࣃࢡ㉁ ࢆ⁐ゎࡋࠊ࣓ࣛࣀࢯ࣮࣒㸦࣓ࣛࢽࣥ㢛 ⢏㸧ࢆᢳฟࡋࡓ [68, 69]ࠋpH 6.86 ࡢࣜࣥ㓟⦆⾪ᾮ 600 gࠊࣃࣃࣥ 45 gࠊࢪࢳ࢚࢜ࣜࢺࣜࢺ࣮ࣝ 6 g ࡢΰྜᾮẟ㧥 20 g ࢆຍ࠼ࠊN2 ୗ 50°C ࡛ 50 hr ᧠ᢾࡋࡓࠋῶᅽୗࠊmembrane filter㸦PTFE
polymer/ADVANTEC cat.No. H020A047A Ꮝᚄ 0.2 μm㸧ࢆ⏝࠸࡚ࢁ
㐣ࡋࠊỈศࡀࡰ↓ࡃ࡞ࡗࡓⅬ࡛࢜ࣥỈࢆ 200 g ຍ࠼࡚᭦ῶ
ᅽℐ㐣ࢆ⾜ࡗࡓࠋḟ࠸࡛iso-Propanol/Hexane/࢜ࣥỈ㸦Vol ẚ 6/6/1㸧
ᾮ 200 g ࢆຍ࠼࡚ῶᅽℐ㐣ࢆ 2 ᅇ⾜ࡗࡓࠋ᭦࢜ࣥỈ 200 g ࢆ
ຍ࠼࡚ῶᅽℐ㐣ࡍࡿᕤ⛬ࢆ 3 ᅇ⧞ࡾ㏉ࡋࠊ60°Cࠊ1 hrࠊ10 cmHg ࡛ῶ
33 / 106
㹙࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ᢳฟ㹛
༢㞳ࡋࡓ࣓ࣛࣀࢯ࣮࣒ࢆάᛶ Sodium dodecyl sulfate ࡢ 5%aq.࡛
Ὑίࡋ࡚࿘㎶⬡㉁ࢆ㝖࠸ࡓࠋḟ࠸࡛㢛⢏ࢆ CHCl3/Methanol㸦Vol ẚ 2/1㸧 ୰࡛ 30 ⛊㛫㉸㡢Ἴฎ⌮ᚋࠊ37°C ࡛ 1 hrࠊᐊ ࡛ 2 ᪥㛫ᨺ⨨ࡋ࡚࣓ ࣛࣀࢯ࣮࣒⤖ྜࡋࡓ⬡㉁ࢆᢳฟࡋࡓࠋ㐲ᚰศ㞳ࢆ⧞ࡾ㏉ࡋ࡚࣓ࣛࣀࢯ ࣮࣒ࢆ㝖ࡁࠊ⤖ྜ⬡㉁ࡢ⁐ᾮࢆᚓࡓࠋ 㹙⬡㉁ศᯒ㹛 ヨᩱࡢ≉ᛶồࡵࡿሗᛂࡌ࡚௨ୗࡢᶵჾศᯒᡭἲࢆ࠸ศࡅࠊ࠶ ࡿ࠸ࡣ⤌ࡳྜࢃࡏ࡚⏝࠸ࡓࠋ࡞࠾ࠊ⬡⫫㓟ࡢᐃ㔞ࡣ C19:0 ⬡⫫㓟ࢆෆ ᶆࡋ࡚⏝࠸ࡓࠋ MS ࣃࢱ࣮ࣥࢆᇶ≀㉁ࡢᵓ㐀ᖐᒓࢆ⾜࠺㝿ࡣࢹ࣮ࢱ࣮࣋ࢫࡋ࡚
Mass Bank http://www.massbank.jp/ ࡞ࢆ⏝࠸ࡓࠋ
㸨FTIR-ATR㸸⬡㉁᳨ฟ⏝࠸ࡓ [64]ࠋ
࣭ᶵჾ㸸ML Agilent 5500 Compact FTIR㸦Agilent Technologies, USA㸧
ࡲࡓࡣ Travel IR㸦Smith Detection Inc., USA㸧ࠋ
ࢲࣖࣔࣥࢻࡢ ATR probe㸦φ 2 mm㸧ࢆ⏝ࡋࡓࠋ
࣭᪉ἲ㸸 ᐃẖ 2㹼3 ᮏࡢẟ㧥ࢆ⏝࠸ࡓࠋࢫ࣌ࢡࢺࣝࡢ⠊ᅖࡣ 4000
㹼750 cm-1ࠊศゎ⬟ࡣ 8 cm-1 ࡋࠊ48 ᅇ✚⟬ࡋ࡚ᚓࡓࢹ࣮ࢱ
34 / 106 㸨TLC㸸࣓ࣛࣀࢯ࣮࣒ࡽᢳฟࡋࡓ⬡㉁ࡢศ⏬⏝࠸ࡓࠋ ヨᩱࡢ CHCl3/Methanol㸦Vol ẚ 1/2㸧⁐ᾮࢆࢩࣜ࢝ࢤࣝ 60 ࡢ TLC ࣉ࣮ࣞࢺ㸦ග⣧⸆㸧ࢫ࣏ࢵࢺࡋ࡚ᒎ㛤ࡉࡏࡓࠋ ᒎ㛤⁐፹ࡣ CHCl3/Methanol㸦Vol ẚ 95/12㸧ࠋᒎ㛤ᚋࡢࣉ࣮ࣞࢺ 50% ◲㓟 aq. ࢆࢫࣉ࣮ࣞࡋࠊ110㹼130°C ຍ⇕ࡋ࡚⬡㉁ࡢ᳨ฟࢆ⾜ࡗࡓࠋ 㸨HPLC㸸࣓ࣛࣀࢯ࣮࣒ࡽᢳฟࡋࡓ⬡㉁ࡢศ㞳࣭ศᯒ⏝࠸ࡓࠋ ࣭ᶵჾ㸸⺯ග᳨ฟ⨨ RF10A-XL㸦ບ㉳Ἴ㛗 350 nmࠊ⺯ගἼ㛗 450 nm ᓥὠ〇సᡤ㸧ࠊ࣒࢝ࣛ Shim-pack XR-DOS㸦100×4.6 mmࠊ40°Cࠊ ᓥὠ〇సᡤ㸧ࠊ࣏ࣥࣉ L-6200 pump㸦᪥❧〇సᡤ㸧 ࣭⁐㞳ᾮ㸸50-100% Methanol/0.1% ࢠ㓟 ࡢ⃰ᗘ໙㓄ᾮࠊὶ㏿ࡣ 0.5 ml/min. 㸨GCMS㸸ẟ⌫ࡢ⬡⫫㓟ࡑࡢㄏᑟయࡢᵓ㐀ゎᯒ⏝࠸ࡓࠋ ࣭ᶵჾ㸸JMS GC-Mateϩ㸦᪥ᮏ㟁Ꮚ㸧
࣒࢝ࣛࡣ capillary high polarity polyethylene glycol column
DB-WAX ࡲࡓࡣ DB-WAXetr㸦Agilent J&W, USA㸧
㸨UPLC-ESI-QToF-MS㸸HPLC ࡛ศ㞳ࡋࡓ⬡㉁ࡢᵓ㐀ゎᯒ⏝࠸ࡓࠋ
࣭ᶵჾ㸸UPLC-ESI-QToF-MS Xevo㸦Waters, USA㸧
࣒࢝ࣛࡣ ACQUITY UPLC BEH C18㸦1.7 μm, 2.1×50 mm㸧
࣭⁐㞳ᾮ㸸50-100% Methanol/0.1% ࢠ㓟 ࡢ⃰ᗘ໙㓄ᾮࠊὶ㏿ࡣ 0.3 ml/min.
35 / 106
MS ࣮ࣔࢻ㸸loading 㟁Ⲵࡣ capillary ᑐࡋ࡚ 3.0 kVࠊsampling cone ᑐࡋ࡚ 40 Vࠊextraction cone ᑐࡋ࡚ 2.5 V MS/MS ࣮ࣔࢻ㸸⾪✺࢚ࢿࣝࢠ࣮ࡣ 20㹼80 V ࡢ⠊ᅖ࡛ࢧࣥࣉࣝ⃰
ᗘᛂࡌ࡚ㄪ⠇ࡋࡓࠋ
㸨ToF-SIMS㸸ẟ㧥⾲ᒙࡽෆ㒊ࡅ࡚ࡢ⬡⫫㓟ࡢศᕸࢆ ᐃࡋࡓ [70-72]ࠋ
࣭ᶵჾ㸸ToF-SIMS ϫinstrument㸦ION-ToF GmbH, Münster, Germany㸧
୍ḟ࢜ࣥࡣ Bi+㸦25 keVࠊ0.3 pA㸧 㸨SEM㸸ẟ㧥⾲㠃ࡢ࣮࢟ࣗࢸࢡࣝ㞳≧ែࢆほᐹࡋࡓࠋ ࣭⏝ᶵჾ㸸SEM JSM6330F㸦᪥ᮏ㟁Ꮚ㸧 ヨᩱࢥ࣮ࢸࣥࢢ⨨ ESC-101㸦࢚ࣜ࢜ࢽࢡࢫ㸧 ࣭᪉ἲ㸸ẟ㧥ヨᩱࢆ┿㘷ࡢ SEM ヨᩱྎ୧㠃ࢸ࣮ࣉ࡛᥋╔ࡋࠊࢱࣥ ࢢࢫࢸࣥ╔㸦ཌࡳ㹼200 Å㸧ࢆ⾜ࡗࡓࠋຍ㏿㟁ᅽ 15 kV ࡛ SEM ほᐹࢆ⾜ࡗࡓࠋ 㸨TEM㸸ẟ㧥ෆ㒊ᵓ㐀ࡢほᐹ⏝࠸ࡓࠋ ࣭ᶵჾ㸸TEM H-7100㸦᪥❧ࣁࢸࢡࣀࣟࢪ࣮ࢬ㸧 ࣑ࢡࣟࢺ࣮࣒ Ultracut N㸦Reichert-Nissei㸧 ࣭᪉ἲ㸸ẟ㧥ࢆ࢚࣏࢟ࢩᶞ⬡㸦Oken Epok 812 ࢭࢵࢺࠊᛂ◊ၟ㸧 ໟᇙࡋࠊ࣑ࢡࣟࢺ࣮࣒࡛ 100 nm ⷧษࠋ㓑㓟࢘ࣛࣥࢡ࢚ࣥ 㓟㖄࡛㔜ᰁⰍᚋࠊTEM ほᐹࢆ⾜ࡗࡓࠋ
36 / 106
㸯㸫㸴㸬⤖ᯝ
㸯㸫㸴㸫㸯㸬ẟᖿ ẟᖿ㒊ศࡢ⬡㉁ศᕸࢆ☜ㄆࡍࡿࡓࡵࠊᮍฎ⌮ẟ㧥ཬࡧ⦪ 2 ศࡋࡓẟ 㧥ࡢ FTIR ᐃࢆ⾜࠸ࠊ๓⪅ࡽࡣẟ㧥⾲㠃ࠊᚋ⪅ࡽࡣẟ㧥ෆ㒊ࡢ ሗࢆᚓࡓࠋ ᐃ⤖ᯝࡢ 2 ḟᚤศࢫ࣌ࢡࢺࣝࡢෆࠊ㧗Ἴᩘ㡿ᇦ㸦2750㹼3100 cm-1㸧ࢆ Figure 8 (A)ࠊపἼᩘ㡿ᇦ㸦900㹼1200 cm-1㸧ࢆ Figure 8 (B)♧ࡋ
ࡓࠋẟ㧥ෆ㒊ࡢ ᐃࢫ࣌ࢡࢺࣝࡢ࡞ࣆ࣮ࢡ▮༳㸦Ќ㸧࡛࣐࣮ࢡࡋࡓࠋ 3010㹼3020 cm-1 ࡢ྾ࡀẟ㧥ෆ㒊࡛ࡣ᫂░ㄆࡵࡽࢀࡓࡀࠊẟ㧥⾲ 㠃࡛ࡣࢇぢࡽࢀ࡞ࡗࡓ㸦Fig. 8 (A)㸧ࠋࡇࡢἼᩘ㡿ᇦࡢ྾ࡣ =C-H ᖐᒓࡉࢀࠊ㣬⬡⫫㓟ࡢᏑᅾࢆ♧ࡋ࡚࠸ࡿࠋࡲࡓࠊ1020 cm-1 ࡢࣆ࣮ࢡࡶẟ㧥ෆ㒊࡛≉ࡁࡃࠊ⾲㠃࡛ᑠࡉ࠸ࡀࡳ࡚ࢀࡓ㸦Fig. 8 (B)㸧ࠋࡇࡢἼᩘ㡿ᇦࡢࣆ࣮ࢡࡣࠊඛࡢ◊✲ [57] ࡛ぢฟࡉࢀࡓ⢾⬡㉁ࡢ ≉ᚩⓗ࡞ࣆ࣮ࢡ୍⮴ࡋ࡚࠸ࡿࠋ௨ୖࡼࡾࠊẟᖿ㒊ศࡢෆ㒊 ࡣ⾲㠃ࡼ ࡾࡶከࡃࡢ㣬⬡⫫㓟⢾⬡㉁ࡀᏑᅾࡍࡿࡀุ᫂ࡋࡓࠋ 1040 cm-1 ㏆ࡢࣆ࣮ࢡࡣ -SO3H ࡢᏑᅾࢆ♧ࡋࠊࢣࣛࢳࣥࢱࣥࣃࢡ ࡢ -SH ᇶࡢ㓟ࡢᗘྜࢆ⾲ࡍ [73]ࠋࡇࡢࣆ࣮ࢡࡣẟ㧥⾲㠃ࡢ᪉ࡀෆ㒊 ࡼࡾࡶࡎࡗࡁ࠸㸦Fig. 8 (B)㸧ࡼࡾࠊẟ㧥⾲㠃ࡢࢣࣛࢳࣥࢱࣥࣃࢡ ࡣෆ㒊ẚ࡚㓟ࡀ㐍ࢇ࡛࠸ࡿࡀࢃࡗࡓࠋ
37 / 106
F
Figure 8 Second derivative FTIR spectra of hair shaft surface and inside of half-cut hair.
38 / 106 㸯㸫㸴㸫㸰㸬ẟᖿࡢ⾲ᒙࠊෆ㒊 ḟẟ㧥ෆ㒊ࡢ㣬⬡⫫㓟ࡢศᕸࢆㄪࡿࡓࡵࠊศẟ᩿㠃ࡢ⾲ ᒙࡽ୰ᚰࡅ࡚ࠊ௨ୗࡢ 3 ⟠ᡤ࡛ ToF-SIMS㸦㣕⾜㛫ᆺḟ࢜ ࣥ㉁㔞ศᯒ㸧 ᐃࢆ⾜ࡗࡓࠋ ࣭࣮࢟ࣗࢸࢡࣝ㹼ࢥࣝࢸࢵࢡࢫ㡿ᇦ㸦ẟ㧥⾲ᒙ㸧 ࣭ࢥࣝࢸࢵࢡࢫ㡿ᇦ ࣭ࢥࣝࢸࢵࢡࢫ㹼࣓ࢹࣗࣛ㡿ᇦ㸦ẟ㧥୰ᚰ㸧 ࠾࠾ࡼࡑࡢ ᐃ⟠ᡤࢆ Figure 9 ♧ࡋࡓࠋ ⤖ᯝࢆ Figure 10 ♧ࡍࠋ3 ࡘࡢ ᐃ㡿ᇦ࡚࠾࠸࡚ࠊ࢜ࣞࣥ㓟 㸦C18:1㸧ࠊࣜࣀ࣮ࣝ㓟㸦18:2㸧ࠊࣜࣀࣞࣥ㓟㸦18:3㸧ࡢࣆ࣮ࢡࡀࡑࢀࡒࢀ m/z = 281.1ࠊ279.1ࠊ277.1 ᫂░᳨ฟࡉࢀࡓࠋࡇࢀࡽࡢࣆ࣮ࢡࡢᙉ ᗘࡣࠊẟ㧥ෆ㒊㸦ࢥࣝࢸࢵࢡࢫ 㡿ᇦཬࡧࢥࣝࢸࢵࢡࢫ㹼࣓ࢹࣗࣛ㡿ᇦ㸧 ࡢ᪉ࡀ⾲ᒙ㸦࣮࢟ࣗࢸࢡࣝ㹼ࢥࣝࢸࢵࢡࢫ㡿ᇦ㸧ࡼࡾࡶࡎࡗࡁࡃࠊ ≉ࣜࣀ࣮ࣝ㓟ࣜࣀࣞࣥ㓟ࡣ⾲ᒙ㏆ࡢ 2 ಸ௨ୖࠊࡑࡋ࡚࢜ࣞࣥ㓟 ࡣ⣙ 1.25 ಸࡔࡗࡓࠋ௨ୖࡼࡾࠊC18 ࡢ㣬⬡⫫㓟ࠊࡾࢃࡅከ౯ 㣬⬡⫫㓟ࡢ C18:2 C18:3 ࡣẟ㧥⾲ᒙࡼࡾࡶෆ㒊ࡢ᪉ࡼࡾከࡃ ศᕸࡋ࡚࠸ࡿࡀุ᫂ࡋࡓࠋ
39 / 106 F Figure 10 ẟ㧥᩿㠃ࡢ ToF-SIMS ࣃࢱ࣮ࣥ ୖࡽ㡰 ࣮࢟ࣗ ࢸ ࢡࣝ 㹼ࢥࣝ ࢸࢵࢡ ࢫ ࠊ ࢥࣝࢸࢵࢡ ࢫࠊࢥ ࣝࢸ ࢵࢡࢫ 㹼࣓ ࢹࣗࣛࡢ㡿 ᇦࡢ࣐ ࢫࢫ ࣌ࢡࢺࣝ ࢆ ♧ࡋ࡚ ࠸ࡿ ࠋ࠸ࡎࢀࡢ 㡿ᇦ ࠾࠸ ࡚ࡶ㣬 ⬡⫫㓟㸦C18:1, C18:2, C18:3㸧ࡢࣆ࣮ࢡࡀ᫂░ㄆࡵࡽࢀࡓࠋ ࢥ ࣝ ࢸࢵ ࢡ ࢫ㹼 ࣓ࢹ ࣗ ࣛ ࢥ ࣝ ࢸࢵ ࢡ ࢫ Figure 99 ศẟ᩿㠃࣮ࣞࢨ㢧ᚤ㙾⏬ീ ToF-SIMS ᐃࢆ⾜ࡗࡓ࠾࠾ࡼࡑࡢ⠊ᅖࢆ㉥ᯟ࡛♧ࡋࡓࠋ ࢟ ࣗ ࣮ࢸ ࢡࣝ 㹼ࢥ ࣝ ࢸࢵ ࢡ ࢫ
40 / 106
㸯㸫㸴㸫㸱㸬࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ⏺㠃
ḟ࠸࡛ẟ㧥⾲ᒙ㡿ᇦࠊ≉ ࣮࢟ࣗࢸࢡࣝࢥࣝࢸࢵࢡࢫࡢ⏺㠃ࡢ⬡ ㉁ศᕸࢆ᳨ウࡍࡿⅭᮍฎ⌮ẟ㸦࣮࢟ࣗࢸࢡࣝ㞳ฎ⌮↓ࡋ㸧࢟ࣗ
࣮ࢸࢡࣝ㞳ẟࡢ FTIR ᐃࢆ⾜ࡗࡓࠋFigure 11 (A) ࣅ࣮ࢬἲ࡛
࣮࢟ࣗࢸࢡࣝࡀ㞳ࡋࡓẟ㧥⾲㠃㸦BD㸸㞳ࣞ࣋ࣝ㸧ࠊ(B) ࣁ ࣈ ࣛ ࢩ ἲ ࡛ ࢟ ࣗ ࣮ ࢸ ࢡ ࣝ ᒙ ࡀ ୰ 㛫 ࡃ ࡽ ࠸ ࡲ ࡛ 㞳 ࡋ ࡓ ẟ 㧥 ⾲ 㠃 㸦TB1㸸㒊ศ㞳ࣞ࣋ࣝ㸧ࡢ SEM ┿ࢆ♧ࡋࡓࠋࡇࡇ࡛⏝ࡋࡓ FTIR ᶵჾ࡛ࡣࣉ࣮ࣟࣈࡢ᥋㠃ࡽ⣙ 0.5 μm ῝࠸㒊ศࡀ ᐃ⠊ᅖࡢ୰ᚰ࡛࠶ ࡿࠋࡼࡗ࡚ࠊTB1 ࡢẟ㧥ࡣ࣮࢟ࣗࢸࢡࣝᒙࡢ୰ᒙࠊTB2 㸦ࡰ 㞳ࣞ࣋ࣝ㸧 BD ࡢẟ㧥࠾࠸࡚ࡣ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ⏺ 㠃㏆ࡀ ᐃࡉࢀ࡚࠸ࡿ⪃࠼ࡽࢀࡿࠋFigure 11 (C) ࡢẟ㧥᩿㠃 TEM ⏬ീ୰ࠊྛࠎࡢ⬺࣮࢟ࣗࢸࢡࣝࣞ࣋ࣝࡢẟ㧥࠾ࡅࡿ࠾࠾ࡼ ࡑࡢ ᐃ⠊ᅖࢆ▮༳㸦 㸧࡛♧ࡋࡓࠋ ࡞࠾ࠊ⤖ᯝࡋ࡚ࠊBD ࡢẟ㧥 TB2 ࡢẟ㧥ࡢ FTIR ࢫ࣌ࢡࢺࣝࡣ ࡰྠᵝ࡛࠶ࡗࡓࠋ
41 / 106
F
Figure 11 ✀ࠎࡢ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ᚋࡢẟ㧥ࡢ㟁㢧┿
㸦A㸧㸦B㸧ࡣẟ㧥⾲㠃ࡢ SEM ⏬ീࠊ㸦C㸧ࡣ⦪᩿㠃ࡢ TEM ⏬ീ 㸦A㸧ࣅ࣮ࢬἲ࡛ฎ⌮ࡋࡓẟ㧥㸦BD㸸㞳ࣞ࣋ࣝ㸧
㸦B㸧ࣁࣈࣛࢩἲ࡛ฎ⌮ࡋࡓẟ㧥㸦TB1㸸㒊ศ㞳ࣞ࣋ࣝ㸧
㸦C㸧ྛࠎࡢ⬺࣮࢟ࣗࢸࢡࣝࣞ࣋ࣝࡢẟ㧥ࡢ FTIR ᐃ⠊ᅖࢆ♧ࡋࡓ ″‒⁞⁙⁛⁖⁛⁓⁞‒⁗⁕⁛‒⁘‒⁚⁓⁛‒‚⁆‷‿‛ ‒
42 / 106 Figure 12 ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ẟ㸦TB2㸧ᮍฎ⌮ẟ⾲㠃ࡢ࣓ࢳ ࣞࣥ㡿ᇦࡢ FTIR 2 ḟᚤศࢫ࣌ࢡࢺࣝࢆ♧ࡋࡓࠋ2850㹼2860 cm-1 ⌧ ࢀࡿ࣓ࢳࣞࣥࡢᑐ⛠ఙ⦰ື྾ࡣ⬡⫫㓟㔞ᙉ࠸┦㛵ࡀ࠶ࡿࡀ▱ࡽ ࢀ࡚࠸ࡿࡀࠊࡇࢀࡣ ⬺࣮࢟ࣗࢸࢡࣝẟࡢ᪉ࡀ᫂ࡽᙉ࠸ࠋࡼࡗ࡚ࠊ ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ ⏺㠃㏆㸦⬺࣮࢟ࣗࢸࢡࣝẟࡢ⾲㠃㸧 ࡣ࣮࢟ࣗࢸࢡࣝᒙ㸦ᮍฎ⌮ẟ⾲㠃㸧ࡼࡾࡶ㔞ࡢ⬡⫫㓟ࡀᏑᅾࡍࡿ ⪃࠼ࡽࢀࠊẟ㧥ෆ㒊ࡣ⾲㠃ࡼࡾࡶከࡃࡢ⬡⫫㓟ࡀᏑᅾࡍࡿ࠸࠺ 㸯 㸫㸴㸫㸯㡯ࡢ⤖ᯝࡀࡅࡽࢀࡓࠋ ḟ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ẟᮍฎ⌮ẟࡢ⾲㠃ࡢ FTIR ࢫ࣌ࢡࢺࣝ ࢆ Figure 13 (A) ♧ࡋࡓࠋୖࡽ㡰ᮍฎ⌮ẟࠊ㒊ศ㞳㸦TB1㸧ẟࠊ ࡰ㞳㸦TB2㸧ẟࡢࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋ1020 cm-1 ࡢࣆ࣮ࢡࡣᮍ ฎ⌮ẟ࡛ࡣぢࡽࢀ࡞ ࡗࡓࡀࠊ࣮࢟ࣗࢸࢡࣝࡢ㞳ࡀ㐍ࡴࡘࢀ࡚ ࡁࡃ࡞ࡗ࡚࠸ࡗࡓࠋ ⬺࣮࢟ࣗࢸࢡࣝẟ㸦TB2㸧ᮍฎ⌮ẟࡢᕪࢫ࣌ࢡࢺࣝࢆ Figure 13 (B) ࡢୖẁ♧ࡋࡓࠋ1020 cm-1 ࡁࡃ᫂░࡞ࣆ࣮ࢡࠊ1120ࠊ1300ࠊ 1370ࠊ1550ࠊ1640 cm-1 ᑠࡉ࠸ࡀ≉ᚩⓗ࡞ࣆ࣮ࢡࡀぢࡽࢀࡓࠋ1020 cm-1 ࡢࣆ࣮ࢡࡣࢢࣝࢥࢧ࣑ࣥྵ᭷≀㉁ࠊ1370㹼1380 cm-1 ࡢࣆ࣮ࢡࡣࢫࢸࣟ ࣮ࣝྜ≀≉ᚩⓗぢࡽࢀࡿࣆ࣮ࢡ࡛࠶ࡿ [74]ࠋཧ⪃ࡢࡓࡵ Figure 13 (B) ࡢ୰ẁୗẁࡑࢀࡒࢀ N-Heptanoyl-glucosamine GlcNAc ᶆရࡢࢫ࣌ࢡࢺࣝࢆ♧ࡋࡓࠋ ௨ୖࡢ⤖ᯝࡣ࣮࢟ࣗࢸࢡࣝࢥࣝࢸࢵࢡࢫࡢ⏺㠃㏆⬡⫫㓟ྵ᭷ ≀㉁ࠊࢢࣝࢥࢧ࣑ࣥྵ᭷≀㉁ࢫࢸ࣮ࣟࣝྵ᭷≀㉁ࡀᏑᅾࡍࡿࢆ♧ࡍ ࡶࡢ࡛࠶ࡾࠊඛẟ㧥ෆ࡛ࡢᏑᅾࡀሗ࿌ [57] ࡉࢀࡓ GlcNAc ྵ᭷ ESG ᵝ⬡㉁ࡢᏑᅾ㒊ࢆᚤ⣽ᵓ㐀࡛ࣞ࣋ࣝ♧ࡍ⤖ᯝ⪃࠼ࡽࢀࡿࠋణࡋࠊ
43 / 106
⌧ᅾࡢゎᯒᢏ⾡࡛ࡣ GalNAc GlcNAc ࢆ༊ูࡍࡿࡣ࡛ࡁ࡞࠸ࡢ
44 / 106 F Figure 12 ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ẟ㸦TB2㸧ᮍฎ⌮ẟࡢ⾲㠃ࡢ࣓ࢳࣞ ࣥ㡿ᇦࡢ FTIR 2 ḟᚤศࢫ࣌ࢡࢺࣝ ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ẟࡢ࣓ࢳࣞࣥࡢᑐ⛠ఙ⦰ື㸦2850㸫2860 cm-1㸧ࢆ▮༳ 㸦 㸧࡛♧ࡋࡓࠋ
45 / 106 Figure 13 ⬺࣮࢟ࣗࢸࢡࣝฎ⌮ẟᮍฎ⌮ẟࡢ⾲㠃ࡢ FTIR ࢫ࣌ࢡ ࢺࣝ㸦ᣦ⣠㡿ᇦ㸧 㸦A㸧ୖࡽ㡰ᮍฎ⌮ẟࠊ㒊ศ㞳㸦TB1㸧ẟࠊࡰ㞳㸦TB2㸧ẟࡢࢫ ࣌ࢡࢺࣝࠋ 㸦B㸧ୖẁࡣࠊ⬺࣮࢟ࣗࢸࢡࣝẟ㸦TB2㸧ࡢ FTIR ࢫ࣌ࢡࢺࣝࡽᮍฎ⌮ẟ ࡢࢫ࣌ࢡࢺࣝࢆᕪࡋᘬ࠸ࡓᕪࢫ࣌ࢡࢺࣝࠋ୰ࠊୗẁࡣࡑࢀࡒࢀ N-Heptanoyl-glucosamine GlcNAc ࡢࢫ࣌ࢡࢺࣝࢆ♧ࡋࡓࠋ (B)
46 / 106 㸯㸫㸴㸫㸲㸬࣓ࣛࣀࢯ࣮࣒ ࡇࡇࡲ࡛ࡢ⤖ᯝࡼࡾࠊ㣬⬡⫫㓟ࡣẟ㧥⾲ᒙ㸦࣮࢟ࣗࢸࢡࣝ㸧 ࡣᑡ࡞ࡃࠊෆ㒊㸦ࢥࣝࢸࢵࢡࢫ㹼࣓ࢹࣗࣛ 㸧ከࡃᏑᅾࡍࡿ࠸࠺ࡀ ุ᫂ࡋࡓࠋẟ㧥⬡㉁ࡀᏑᅾࡍࡿࡢࡣ CMC ࡸ⣽⬊⭷࡞⤌⧊ࡢ⏺㠃 ⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊ࣮࢟ࣗࢸࢡࣝࡣࢇᏑᅾࡋ࡞࠸ࡀࢥࣝ ࢸࢵࢡࢫࡸ࣓ࢹࣗࣛከࡃᏑᅾࡍࡿ⤌⧊ࡋ࡚࣓ࣛࣀࢯ࣮࣒ὀ┠ࡋࠊ ࡑࡢ⤖ྜ⬡㉁ࡢศᯒࢆ⾜ࡗࡓࠋ ࡲࡎ࣓ࣛࣀࢯ࣮࣒ࡼࡾᢳฟࡋࡓ⬡㉁ࡢ TLC ศᯒࡼࡗ࡚ࠊẟ㧥ෆࡢ Ꮡᅾࡀ᪤ሗ࿌ࡉࢀ࡚࠸ࡓࢢࣜࢥࢩࣝࢭ࣑ࣛࢻ ᵝ⬡㉁ [57] ࢆ᳨ฟࡋࡓࠋ ᭦ࠊHPLC ࡛ศ㞳ศᯒࡋࡓ⏬ศࡢ FTIR ᐃࡼࡾ Figure 14 ♧ ࡍࢫ࣌ࢡࢺࣝࢆᚓࡓࠋ࢚ࢫࢸࣝࡸ࣑ࢻ I ࡢ C=O ྾࡞ࢭ࣑ࣛࢻ ≉ᚩⓗ࡞㉥እ྾ࢆ♧ࡋ࡚࠸ࡿ ࠋࢭ࣑ࣛࢻᵓ㐀ࡢᏑᅾࡘ࠸࡚ࡣ MS/MS ࣃࢱ࣮ࣥࢆᇶゎᯒࡋࡓ⤖ᯝࢆᚋ㏙ࡍࡿࠋ ࡇࡢศ⏬ヨᩱࢆ UPLC-ESI-QToF-MS ศᯒࡋࡓࡇࢁࠊm/z = 885 907 ศᏊ࢜ࣥࣆ࣮ࢡࡀ᳨ฟࡉࢀࡓ㸦Fig. 15㸧ࠋm/z = 885 ࡣỈ⣲ ࢜ࣥຍ㸦M+H+㸧ࠊm/z = 907 ࡣࢼࢺ࣒ࣜ࢘࢜ࣥຍ㸦M+Na+㸧ࡢศ Ꮚ࢜ࣥࣆ࣮ࢡ⪃࠼ࡽࢀࡿࡼࡾࠊࡇࡢ⬡㉁ࡢศᏊ㔞ࢆ 884 ᥎ ࡋ ࡓࠋ
47 / 106
F
Figure 14 ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡢ୍㒊ࡢ FTIR ࢫ࣌ࢡࢺࣝ
48 / 106
F
49 / 106 ḟࠊMS/MS ࡼࡾヲ⣽࡞ᵓ㐀ྠᐃࢆ⾜ࡗࡓࠋ m/z = 885 ࡢࢱ࣮ࢤࢵࢺࣆ࣮ࢡᑐࡍࡿ positive ࣮ࣔࢻࡢ MS/MS ࣃࢱ࣮ࣥࢆ Figure 16 (A) ♧ࡍࠋMS/MS ศᯒࡢ㝿ࡢࣇࣛࢢ࣓ࣥࢸ࣮ ࢩࣙࣥࡼࡗ࡚⏕ᡂࡋࡓ⪃࠼ࡽࢀࡿ m/z = 119 ࡢࣇࣛࢢ࣓ࣥࢺ࢜ࣥ ࡢࣆ࣮ࢡࡀほ ࡉࢀࡓࠋᙉ࠸⾪✺࢚ࢿࣝࢠ࣮㸦80V㸧ࢆ࠼ࡓሙྜ m/z = 83 ࡢࣆ࣮ࢡࡀ⏕ࡌࡓࡼࡾࠊỈ 2 ศᏊࡀ⬺㞳ࡋࡓ㸦119㸫83 = 36㸧 ᥎ ࡋࠊࡑࢀࢆᇶࢪࣄࢻࣟ࢟ࢩᆺࡢ▷㙐ࣝ࢟ࣝศᏊ㸦Ma㸧ࡢỈ⣲ ຍ࢜ࣥ㸦Ma+H+㸧ࡢᵓ㐀ࢆᑟࡁฟࡋࡓࠋࡑࡢࡢᑠࣆ࣮ࢡ⩌㸦Fig. 16 (A')㸧 ࡢ m/z ್ ࠶ ࢃ ࡏ ࡚ ᭦ ᖐ ᒓ ࢆ ⾜ ࠸ ࠊ ௨ ୗ ࡢ ᰿ ᣐ ᇶ ࡙ ࠸ ࡚ Figure 16 (B) ♧ࡍỈ㓟⬡⫫㓟๓㥑యࣝࢹࣄࢻ㸦Mb, m/z = 204㸧 ࡢᵓ㐀ࢆᑟ࠸ࡓࠋ ࣭m/z = 119ࠊ133ࠊ163 ࡢࣆ࣮ࢡࡣ Mb ࡀ◚⥺࡛♧ࡋࡓ⨨࡛㛤ࡋ࡚ ⏕ࡌࡓ MaࠊMcࠊMd ࡢỈ⣲ຍࣇࣛࢢ࣓ࣥࢺ࢜ࣥᖐᒓࡉࢀࡿࠋ ࣭m/z = 227 ࡢࣆ࣮ࢡࡣ Mb ࡢ Na+ ຍศᏊ࢜ࣥࠊm/z = 205 ࡢࣆ ࣮ࢡࡣ H+ ຍศᏊ࢜ࣥᖐᒓࡉࢀࡿࠋ ࣭m/z = 177 ࡢࣆ࣮ࢡࡣ Mb ศᏊࡽࣝࢹࣄࢻࡀ⬺㞳ࡋࡓ Me ࣇࣛ ࢢ࣓ࣥࢺᖐᒓࡉࢀࡿࠋ ௨ୖࡼࡾࠊ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡣࡑࡢศᏊᵓ㐀ࡢ୍㒊ࡋ࡚ 3, 6, 8-ࢺࣜࣄࢻࣟ࢟ࢩࣝࢹ࢝ࣥ㓟ࢆྵࡴ⪃࠼ࡽࢀࡿࠋ ᭦ࠊ࣓ࢳࣝᇶᮎ➃ࡽᩘ࠼࡚ 3 OH ᇶࡀᏑᅾࡍࡿࡼࡾࠊn-3 㣬 ⤖ྜ ࢆ ࡶ ࡘ α ࣜࣀࣞࣥ㓟 ALA ⏤᮶ࡢỈ㓟≀࡛࠶ࡿ ࠸࠺ྍ⬟ᛶࡀ♧ࡉࢀࡓࠋࠋ
50 / 106 F Figure 16 ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡢ MS/MS ࣃࢱ࣮ࣥཬࡧ᥎ ᵓ㐀ᅗ 㸦A㸧m/z = 885 ࡢࢱ࣮ࢤࢵࢺ࢜ࣥࡢ MS/MS ࢫ࣌ࢡࢺࣝࠋm/z = 119.1 ࡢᙉ ࠸࢜ࣥࣆ࣮ࢡࡣ m/z 118.1 ࡢࣇࣛࢢ࣓ࣥࢺ㸦Ma㸧ࡢỈ⣲࢜ࣥຍయ ⪃࠼ࡽࢀࡿࠋMa㸦m/z = 118.1㸧ࢆ⬡㉁ࡢ⬡⫫㓟㒊ศ⏤᮶ࡍࡿࢪࣄࢻ ࣟ࢟ࢩ C6 ࣝ࢝ࣥ᥎ ࡋࠊࡑࡢᵓ㐀ࢆ♧ࡋࡓࠋ 㸦A'㸧A ♧ࡋࡓࢫ࣌ࢡࢺࣝࡢෆࠊm/z = 130㹼230 ࡢᑠࣆ࣮ࢡ⩌ࢆᣑࡋ࡚♧ ࡋࡓࠋ 㸦B㸧A ཬࡧ A' ࡢࣇࣛࢢ࣓ࣥࢺ࢜ࣥࣆ࣮ࢡࢆᇶᑟࡁฟࡋࡓỈ㓟⬡⫫㓟๓ 㥑యࣝࢹࣄࢻ㸦Mb, m/z = 204㸧ࡢ᥎ ᵓ㐀ࠋMS/MS ᐃ㉳ࡁࡿࣇ ࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࡢ⨨ࢆ◚⥺࡛♧ࡋࡓࠋ
51 / 106 TLC ཬࡧ FTIR ࡢ⤖ᯝࡼࡾࠊ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡣࢭ࣑ࣛࢻᵓ 㐀ࡀྵࡲࢀࡿࡢ࡛ࡣ࡞࠸᥎ ࡉࢀࡿࠋࡑࡇ࡛ࠊ⓶ከࡃᏑᅾࡍࡿ ࢭ࣑ࣛࢻࡢ୍✀࡛࠶ࡿ 4-Hydroxysphinganine ࡢᏑᅾࢆ๓ᥦࡋ࡚ࢱ࣮ ࢤࢵࢺ࢜ࣥࣆ࣮ࢡ m/z = 885 ࡢ MS/MS ࣃࢱ࣮ࣥࡢᖐᒓࢆ⾜ࡗࡓ ࡇࢁࠊm/z = 377ࠊ495 ࡢ࣐ࢫࣆ࣮ࢡ㸦Fig. 17 A㸧ࢆᇶ௨ୗࡢ᥎ㄽࢆ ᚓࡓࠋ MaࠊMb ᵓ㐀ࢆྵࡴࢭ࣑ࣛࢻࡀࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࢆ㉳ࡇࡋࡓሙྜ ⏕ᡂࡍࡿศᏊ࢜ࣥࡢೃ⿵ࡋ࡚ࠊFigure 17 B ࡢ Cer1 ࡢᵓ㐀ࡽ ⬺ỈࠊNa+ ຍࡋࡓ≀㉁㸦m/z = 495㸧ࡀ⪃࠼ࡽࢀࡿࠋ᭦⬡⫫㓟ࡢ୍㒊 㸦Ma㸧ࡀ⬺㞳ࡋࠊH+ ຍࡋࡓศᏊ࢜ࣥ㸦m/z = 377㸧ࡶ⪃࠼ᚓࡿࠋࡇ ࡢ᥎ㄽࡣࢭ࣑ࣛࢻࡢᏑᅾࡢ☜ド࡛ࡣ࡞࠸ࡶࡢࡢࠊᏑᅾࡋᚓࡿᵓ㐀ࡢೃ⿵ ࡋ࡚ᣲࡆ࡚࠾ࡃࠋ ᭦ࠊm/z = 230㹼320 ࡢࣆ࣮ࢡ⩌ࢆᇶࡋ࡚ྠᵝᵓ㐀ࡢᖐᒓࢆ⾜ ࡗࡓࠋࡑࡢ⤖ᯝࠊFigure 18 ♧ࡍࢫࣇࣥࢦࢻሷᇶỈ㓟⬡⫫㓟 ࡀ࣑ࢻ⤖ྜࡋࡓᵓ㐀ཬࡧࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࡼࡗ࡚⏕ᡂࡋࡓࣝ ࢹࣄࢻయࡢᵓ㐀ࡀᑟࢀࡓࡼࡾࠊࢭ࣑ࣛࢻࡢᏑᅾࡀ᥎ ࡉࢀࡓࠋ ௨ୖࠊ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡣࡑࡢᵓ㐀ࡢ୍㒊Ỉ㓟⬡⫫㓟ࢆྵࡳࠊ ࡘࡑࢀࡀࢭ࣑ࣛࢻࡸࢫࣇࣥࢦࢻ⤖ྜࡋ࡚࠸ࡿྍ⬟ᛶࢆ♧ࡍ⤖ᯝ ࢆᚓࡓࠋ
52 / 106 F Figure 17 ࢭ࣑ࣛࢻᵓ㐀ࢆྵࡴ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡢᵓ㐀ೃ⿵ Figure 18 ࢫࣇࣥࢦࢻࢆྵࡴ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡢᵓ㐀ೃ⿵ A B
53 / 106 㸯㸫㸴㸫㸳㸬ẟ⌫ ࣓ࣛࣀࢯ࣮࣒ࡣẟ⌫ࡢ࣓ࣛࣀࢧࢺ࡛⏕ྜᡂࡉࢀࡿࠋ㸯㸫㸴㸫㸲 㡯࡛ グࡋࡓᵝࠊ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡀࡑࡢᵓ㐀ࡢ୍㒊ࡋ࡚Ỉ㓟ࢹ࢝ ࣥ㓟ࢆྵࡴࡢ࡞ࡽࡤࠊẟ⌫ෆỈ㓟⬡⫫㓟ࡀᏑᅾࡋ࡚࠸ࡿ⪃࠼ࡽࢀ ࡿࠋࡑࡇ࡛ࠊẟ⌫ࡽᢳฟࡋࡓ⬡㉁ࢆ DMOX ㄏᑟయࡋࠊᵓ㐀ྠᐃࢆ ⾜ࡗࡓࠋGCMS ࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࢆ Figure 19 (A) ♧ ࡍࠋ᭦ࠊC18 ⬡⫫㓟ㄏᑟయࡢࣆ࣮ࢡࡀฟ⌧ࡍࡿಖᣢ㛫⠊ᅖࡢࢺ࣮ࢱ ࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࢆ Figure 19 (B) ࡢୖẁࠊDMOX ㄏᑟయࡢ≉ ᚩ࡛࠶ࡿ m/z = 113ࠊ126 ࡢࣇࣛࢢ࣓ࣥࢺ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࢆ୰ẁࠊ
ୗẁ♧ࡋࡓࠋScan number 954 ࡢࣆ࣮ࢡ㸦Fig. 19 (B) ▮༳࡛♧ࡋ
ࡓ㸧ࡀ DMOX ㄏᑟయࡢ≉ᚩࢆ᭷ࡋ࡚࠸ࡓࠋࡑࡢ࣐ࢫࢫ࣌ࢡࢺࣝࢆ Figure 20 (A) ♧ࡍࠋࡇࡇ࡛ほ ࡉࢀࡓศᏊ࢜ࣥ㸦m/z = 333㸧ཬࡧ ࡢࣇࣛࢢ࣓ࣥࢺ࢜ࣥࣃࢱ࣮ࣥࡽᑟ࠸ࡓ᥎ ᵓ㐀ࢆ Figure 20 (B) ♧ࡍࠋࡇࢀࡼࡾࠊẟ⌫୰ C17:3 n-6㸦6 ࣄࢻࣟ࢟ࢩ㸦ࡲࡓࡣ 6 ࢣࢺ㸧 (5), 8, 11㸦(E), Z, Z㸧࣊ࣉࢱࢹ࢝ࢺ࢚ࣜࣥ㓟ࡢ㓟≀ࠊࡑࡋ࡚࠾ࡑࡽ ࡃࡣࡑࡢࢣࢺ㸫࢚ࣀ࣮ࣝኚ␗ᛶయ㸦Fig. 20 (C)㸧ࡀᏑᅾࡍࡿ࠸࠺ ྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋࡇࢀࡽࡣࢭࣂࣞࣥ㓟㸦C18:2㸦Δ5, 8㸧㸧ࡲࡓࡣ γ ࣜ ࣀࣞࣥ㓟㸦C18:3㸦Δ6, 9, 12㸧㸧ࡽⅣ⣲ࡀ୍ಶእࢀࡓ≀ࠊࡲࡓࡣࣛ ࢟ࢻࣥ㓟㸦C20:4n-6㸧⏤᮶ࡢ࢚ࢥࢧࣀࢻ௦ㅰ≀⏤᮶≀㉁࡛ࡣ࡞࠸ ᥎ ࡉࢀࡿࠋࡋࡋࠊẟ⌫࡛ࡣከ౯㣬⬡⫫㓟ࡀࡈࡃᑡ㔞ࡋ᳨ฟ ࡉࢀ࡞࠸ࡢ࡛ࠊࡇࢀࡽࡢከ౯㣬⬡⫫㓟㸦C18:2ࠊC18:3ࠊC20:4㸧ࡣ ㏿ࡸẟ⌫࡛௦ㅰࡉࢀࡿࠊࡲࡓࡣ㏿ࡸẟᖿ㍺㏦ࡉࢀࡿ ⪃࠼ ࡽࢀࡿࠋ
54 / 106 F Figure 19 ẟ⌫୰ࡢ⬡⫫㓟-DMOX ㄏᑟయࡢ GCMS ࢫ࣌ࢡࢺࣝ 㸦A㸧⬡⫫㓟-DMOX ㄏᑟయࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࣃࢱ࣮ࣥࠋ࡞⬡ ⫫㓟㸦C16:0, C18:0, C22:1㸧࣐࣮࢟ࣥࢢࡋࡓࠋ 㸦B㸧ಖᣢ㛫 11㹼16 ศࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛ m/z = 113, 126 ࡢ࣐ࢫࢡ࣐ࣟࢺࢢ࣒ࣛࠋScan number 954 ࡢࣆ࣮ࢡ▮༳࡛࣐࣮࢟ࣥࢢࡋ ࡓࠋ C16:0 C18:0 C22:1 (A) C16:0 C18:0 C18:㸯 (B)
55 / 106
F
Figure 20 ẟ⌫୰ࡢ⬡⫫㓟-DMOX ㄏᑟయࡢ scan number 954 ࡢࣆ࣮ ࢡࡢ࣐ࢫࢫ࣌ࢡࢺࣝ᥎ᐃᵓ㐀
㸦A㸧GCMS ࡢ scan number 954 ࡢࣆ࣮ࢡࡢ࣐ࢫࢫ࣌ࢡࢺࣝࠋm/z = 333
ศᏊ࢜ࣥ M+ ࡢࣆ࣮ࢡࡀ᳨ฟࡉࢀࡓࠋ 㸦B㸧A ࡢࣇࣛࢢ࣓ࣥࢺࣃࢱ࣮ࣥࡽᑟࢀࡓ⬡⫫㓟-DMOX ࡢ᥎ ᵓ㐀ࠋ 㸦C㸧⬡⫫㓟㓟≀ࡢኚ␗ᛶయࠋB ࡣ 6-hydroxy-Δ5t ࡢᵓ㐀ࢆ♧ࡋࡓࡀࠊ C ࡢᵝࢣࢺయᖹ⾮≧ែࢆࡗ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋ D (B) (A) (C)
56 / 106 ḟ࠸࡛ࠊ1㹼3 ಶࡢỈ㓟ᇶࡸ㣬⤖ྜࢆ᭷ࡍࡿỈ㓟ࢹ࢝ࣥ㸦ࡲࡓࡣ ࢹࢭࣥ㸧㓟㢮ࡢᏑᅾࢆ๓ᥦࡋ࡚ࠊC10 ⬡⫫㓟ࡀ㏻ᖖ᳨ฟࡉࢀࡿಖᣢ 㛫⠊ᅖࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛ 㸦Fig. 21 (A)㸧ὀ┠ࡋࡓࠋ DMOX ㄏᑟయࡢ≉ᚩ࡛࠶ࡿ m/z = 113ࠊ126 ࡢࣇࣛࢢ࣓ࣥࢺ࢜ࣥࢡ ࣐ࣟࢺࢢ࣒ࣛཬࡧ m/z = 257 ࠾࠸࡚ scan number 605 ࣆ࣮ࢡࡀほ ᐹࡉࢀࡓ㸦Fig. 21 (A) ▮༳࡛♧ࡋࡓ㸧ࠋࡇࡢࣆ࣮ࢡࡢ࣐ࢫࢫ࣌ࢡࢺࣝ ࢆ Figure 21 (B) ♧ࡍࠋࡇࡇ࡛ࡢศᏊ࢜ࣥࣆ࣮ࢡࡣ m/z = 256ࠊ257 ࡢ࠸ࡎࢀ⪃࠼ࡽࢀࡿࡀࠊDMOX ㄏᑟయࡉࢀࡓ⬡⫫㓟ࡢศᏊ࢜ࣥ ࡣ㏻ᖖወᩘ࡞ࡢ࡛ 257 ࡢ᪉⪃࠼ࠊࣇࣛࢢ࣓ࣥࢺࣃࢱ࣮ࣥࢆయ⣔ⓗゎ 㔘ࡋ࡚᥎ ࡋࡓᵓ㐀ࢆ Figure 21 (C) ♧ࡋࡓࠋMS ࡢ㝿 6, 8-ࣄࢻࣟ ࢟ࢩࣝࢹ࢝ࣥ㓟-DMOX㸦M = 257.4㸧ࡽỈ㓟ᇶࡀ 2 ࡘእࢀ㸦Δ18, Δ18; 257.0Ѝ239.0Ѝ220.9㸧ࠊḟᮎ➃ࡢ࣓ࢳࣝᇶࡀእࢀࡿ㸦Δ15; 220.9Ѝ 205.9㸧ࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࡀ㐃⥆ࡋ࡚㉳ࡁࡓ⪃࠼ࠊᅗ୰Ⅼ⥺࡛ࣇ ࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥ ࡢ⨨ࢆ♧ࡋࡓࠋ m/z = 256 ࡢࣆ࣮ࢡࡘ࠸࡚ࡣࠊ௨ୗࡢ 2 ࡘࡢྍ⬟ᛶࡀᣲࡆࡽࢀࡿࠋ ձ⬡⫫㓟-DMOX ㄏᑟయ࡛ࡣ࡞ࡃఱࡽࡢࢥࣥࢱ࣑㸦࠼ࡤࠊDMOX ㄏ ᑟయࡉࢀࡎṧࡗࡓ C15:0 ࣓ࢳ࢚ࣝࢫࢸࣝࡢศᏊ࢜ࣥ㸧࡛࠶ࡿࠋ m/z = 256 ࡢ࣐ࢫࢡ࣐ࣟࢺࢢ࣒ࣛぢࡽࢀࡿࣆ࣮ࢡࡣ scan number 604 ࡛࠶ࡗ࡚ DMOX ㄏᑟయ≉ᚩⓗ࡞ m/z = 113 ࡸ 126 ぢࡽࢀ
ࡿ scan number 605 ࡢࣆ࣮ࢡࡣ␗࡞ࡿ㸦Fig. 21 (A)㸧ࡼࡾࠊࡇࡢ
ྍ⬟ᛶࡣ㧗࠸ࠋ
ղྠࡌᩘࡢỈ㓟ᇶࢆ᭷ࡍࡿࢹ࢝ࣥ㓟ࢹࢭࣥ㓟㸦6,8-hydroxy-Δ7t-; FW
= 255.4㸧ࡢ㠀ඹ᭷⤖ྜᆺ㸦Ỉᛶ⤖ྜࡸỈ⣲⤖ྜ࡞ẚ㍑ⓗ⦆࠸⤖ྜᆺ㸧 ࡢᖹᆒ್㸦m/z = 255ࠊ257 ࡢᖹᆒ࡛ 256㸧࡛࠶ࡿࠋࡋࡋࠊࡇࡕࡽࡢྍ
57 / 106 ⬟ᛶࡣప࠸ᛮࢃࢀࡿࠋ ௨ୖࡢⅬࡣࠊᚋࡢ◊✲࠾࠸࡚᫂ࡽࡋ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ ࢹ࢝ࣥ㓟ࡢ࣓ࢳࣝᇶᮎ➃ࡽ 3 ␒┠ࡢ⨨Ỉ㓟ᇶࡀ⤖ྜࡋ࡚࠸ࡿ ࡼࡾࠊỈ㓟๓ࡢ⬡⫫㓟࡛ࡣ n-3 ࡢ⨨㸦ω3㸧㔜⤖ྜࡀᏑᅾࡋ࡚ ࠸ࡓ᥎ ࡉࢀࡿࠋ༶ࡕࠊALA ࡢࡼ࠺࡞ n-3 ከ౯㣬⬡⫫㓟ࡢ௦ㅰ ≀ࡀẟ⌫࣓ࣛࣀࢯ࣮࣒ࡢ୧᪉Ꮡᅾࡋࠊ௦ㅰ≀ࡢ୍ࡘࡣ࠾ࡑࡽࡃỈ㓟 C10 ⬡⫫㓟࡛࠶ࡿ⪃࠼ࡽࢀࡿࠋ
58 / 106 F Figure 21 ẟ⌫୰ࡢ⬡⫫㓟-DMOX ㄏᑟయࡢ࢜ࣥࢡ࣐ࣟࢺࢢ࣒ࣛࠊ࣐ ࢫࢫ࣌ࢡࢺࣝࠊ᥎ᐃᵓ㐀 㸦A㸧C10 㙐ࡀ㏻ᖖ᳨ฟࡉࢀࡿಖᣢ㛫ࡢ⠊ᅖࡢࢺ࣮ࢱࣝ࢜ࣥࢡ࣐ࣟࢺࢢࣛ ࣒ m/z = 113, 126, 256, 257 ࡢ࣐ࢫࢡ࣐ࣟࢺࢢ࣒ࣛࠋ▮༳ࡣ m/z = 113, 126, 257 ࡢ࣐ࢫࢡ࣐ࣟࢺࢢ࣒ࣛ࠾ࡅࡿ scan number 605 ࡢࣆ࣮ࢡ ⨨ࢆ♧ࡍࠋm/z = 256 ࡢࣆ࣮ࢡ⨨ࡣ scan number 604ࠋ 㸦B㸧scan number 605 ࡢ࣐ࢫࢫ࣌ࢡࢺࣝࠋ㔜せ࡞࣐ࢫࣆ࣮ࢡᕪ࣐࣮࢟ࣥࢢ ࡋࡓࠋ 㸦C㸧B ࡛♧ࡋࡓࣇࣛࢢ࣓ࣥࢺ࢜ࣥࣃࢱ࣮ࣥࡽᑟ࠸ࡓ 6,8-ࢪࣄࢻࣟ࢟ࢩࢹ ࢝ࣥ㓟-DMOX ㄏᑟయࡢᵓ㐀ࠋ◚⥺࡛♧ࡋࡓ⨨࡛㛤ࡀ㉳ࡁࠊB ࡛ほ ࡉࢀࡓ࣐ࢫࣆ࣮ࢡᕪ㸦Δ18, Δ18, Δ15㸧ࡀ⏕ࡌࡓ⪃࠼ࡽࢀࡿࠋ
59 / 106
㸯㸫㸵㸬⪃ᐹ
ࢫࢸࣜࣝࢢࣜࢥࢩࢻ ᵝ⬡㉁ࡣ㏻ᖖࡣ᳜≀ࠊ⸴ࠊ⳦ࡸప⣭┿᰾⏕≀ぢ ࡽࢀࡿ [75] ࡀࠊ⛥ࣄࢺࡢ⫢⮚ࡢ⣽⬊ࡸ⧄⥔ⱆ⣽⬊࠾࠸࡚ࡶᏑᅾࡀ ᣦࡉࢀ࡚࠸ࡿ [76-78]ࠋ⧄⥔ⱆ⣽⬊ࡢࢫࢸࣜࣝࢢࣜࢥࢩࢻࡣࣄ࣮ࢺࢩ ࣙࢵࢡࢱࣥࣃࢡㄏᑟ࡞ࡢࢫࢺࣞࢫᛂ⟅ࢩࢢࢼࣝኚࡢึᮇẁ㝵࡛࣓ࢹ ࢚ࢱ࣮ࡋ࡚ാࡃࡀሗ࿌ࡉࢀࡓࠋẟ㧥࠾࠸࡚ࡶ GlcNAc㸦ࡲࡓ ࡣ GalNAc㸧ྵ᭷ࢫࢸࣜࣝࢢࣜࢥࢩࢻᵝ⬡㉁ࡢᏑᅾࡀሗ࿌ࡉࢀ࡚࠸ࡿ [57]ࠋᮏሗ࡛ࡣࡑࡢ GlcNAc㸦ࡲࡓࡣ GalNAc㸧ྵ᭷⬡㉁ࡢᑡ࡞ࡃࡶ୍ 㒊ࡣẟᖿࡢ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ⏺㠃㎶ࡾᏑᅾࡍࡿࢆ♧ࡋ ࡓࠋ ࡇࡢ⬡㉁ࡣࡢᵝ࡞ᙺࢆᢸ࠺ࡢࡔࢁ࠺ࠋ ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ㛫ࠊ࣮࢟ࣗࢸࢡࣝ㸫࣮࢟ࣗࢸࢡࣝ 㛫ࡑࡋ࡚ࢥࣝࢸࢵࢡࢫ⣽⬊㛫࠸ࡎࢀࡢ⏺㠃ࡶ CMC ࡀᏑᅾࡍࡿࠋࡇࢀ ࡽࡣእほ≧ఝ㏻ࡗ࡚ ࡣ࠸ࡿࡶࡢࡢࠊࡑࡢᛶ≧᫂ࡽ࡞ᕪ␗ࡀ࠶ࡿࡀ ሗ࿌ࡉࢀ࡚࠸ࡿ [36, 79, 80]ࠋ࠼ࡤࠊCao ࡽࡣẟ㧥ࢆᒀ⣲࡛ฎ⌮ࡋ࡚ ࣮࢟ࣗࢸࢡࣝࢆぢࡅୖ↓യ࡞⟄ࡢᵝ࡞ᙧ࡛ẟᖿࡽࡍࡗࡱࡾྲྀࡾ እࡋࡓࠋᙼࡽࡣࢥࣝࢸࢵࢡࢫ࣮࢟ࣗࢸࢡࣝࡢ㛫ࡢ CMC ࡀᒀ⣲ࡼ ࡗ࡚⁐ゎࡋࡓⅭ⤖ྜᛶࡀኻࢃࢀ࡚࣮࢟ࣗࢸࢡࣝࡀእࢀࡓ⪃࠼ࠊ࢟ ࣮ࣗࢸࢡࣝ㸫࣮࢟ࣗࢸࢡࣝ 㛫 CMC ࡼࡾࡶ࣮࢟ࣗࢸࢡࣝ㸫ࢥࣝ ࢸࢵࢡࢫ⏺㠃ࡢ CMC ࡢ᪉ࡀࡇࡢฎ⌮ᑐࡋ࡚⬤࠸᥎ ࡋࡓࠋ ᒀ⣲ࡣỈ⣲⤖ྜࢆ◚ቯࡍࡿാࡁࡢᙉ࠸≀㉁࡛࠶ࡿࠋCao ࡽࡢ⤖ᯝࡣ GlcNAc ྵ᭷ࢫࢸࣜࣝࢢࣜࢥࢩࢻᵝ⬡㉁ࡢᵝỈ⣲⤖ྜ㇏ᐩ࡞⬡㉁ࡀ࢟ ࣮ࣗࢸࢡࣝ㸫ࢥࣝࢸࢵࢡࢫ⏺㠃Ꮡᅾࡍࡿ࠸࠺ᮏ◊✲ࡢ⤖ᯝ▩┪60 / 106 ࡋ࡞࠸ࠋࡇࡢ⬡㉁ࡣ⏺㠃ࡢ⤖ྜࢆᙉࡵ࡚ ࣮࢟ࣗࢸࢡࣝࡢࢥࣝࢸࢵࢡࢫ ᥋╔ᛶࢆ⥔ᣢࡍࡿᶵ⬟ࢆᯝࡓࡋ࡚࠸ࡿࡢࡶࡋࢀ࡞࠸ࠋ ᚲ㡲⬡⫫㓟ࡢࣜࣀ࣮ࣝ㓟ࡸ ALA ࡞ࡣ⏕⌮ᶵ⬟⥔ᣢᴟࡵ࡚㔜せ࡛ ࠶ࡿࡶ㛵ࢃࡽࡎࠊࣄࢺయෆ࠾ࡅࡿ௦ㅰືែ ࡀᮍࡔࢇゎ᫂ࡉࢀ ࡚࠸࡞࠸ࠋ୍᪉ࠊࣄࢺ௨እࡢື≀࡛ࡣከࡃࡢሗ࿌ࡀ࡞ࡉࢀ࡚࠸ࡿ [81-85]ࠋ ࠼ࡤࠊྠ⤒㊰࠾࠸࡚ࡇࢀࡽࡢ C18 PUFA ࡣࡑࢀࡒࢀࣛ࢟ࢻࣥ 㓟㸦C20:4n-6㸧ࡸࢻࢥࢧ࣊࢟ࢧ࢚ࣥ㓟㸦C22:6n-3㸧ࢆྵࡴ C20ࠊC22 PUFA ኚࡉࢀࠊ␗㸦ศゎ㸧⤒㊰࠾࠸࡚ࡣ β 㓟ࡉࢀࡿࠋALA ࡢ β 㓟 ⬺㣬ࡣ㏿ࡸ㐍⾜ࡋࠊయෆ᳨࡛ฟࡉࢀࡿ㔞ࡀᑡ࡞࠸ࡢࡣࡑࡢࡓ ࡵㄝ᫂ࡉࢀࡿࠋ᭦ Fu Sinclair ࡣࣔࣝࣔࢵࢺࡀᦤྲྀࡋࡓ ALA ࡀ㏿ࡸ㢌㒊ࡢ⓶యẟ⛣⾜ࡍࡿࢆሗ࿌ࡋࡓ [63]ࠋࡶࡋࡑࢀࡀ ࣄࢺࡶ࠶࡚ࡣࡲࡿ࡞ࡽࠊᦤྲྀࡋࡓ ALA ࡣ㢌⓶㢌㧥㏿ࡸ⛣⾜ ࡍࡿ⪃࠼ࡽࢀࡿࠋ ẟ㧥Ꮡᅾࡍࡿ ALA 㔞ࡣ࡚ࡶᑡ࡞࠸㸦㸯㸫㸴㸫 㸰 㡯࡛♧ࡋࡓᵝࣜࣀ࣮ࣝ㓟ࡸ࢜ࣞࣥ㓟ࡼࡾࡶᑡ࡞࠸㸧ࡽࠊ⛣⾜ ᚋ㏿ࡸ௦ㅰ㸦β 㓟㸧ࡉࢀ࡚ࡋࡲ࠺⪃࠼ࡽࢀࡿࠋࡣ࠸࠼ࠊALA ࡀ ᦤྲྀᚋ┤ࡕ㢌⓶ࡸẟ㧥⛣⾜ࡍࡿ⌮⏤ࡣㅦ࡛࠶ࡿࠋᚑ᮶ࡢㄝ࡛ࡣࢭ ࢳࣝ CoA ࢆ⏕ᡂࡋ࡚࢚ࢿࣝࢠ࣮ࢆ౪⤥ࡍࡿࡀ࡞ᙺࡉࢀ࡚࠸ࡿ ࡀࠊࡑࢀࡔࡅ࡛࠶ࢁ࠺㸽 ᮏ◊✲࡛ࡣ ALA ࡀ௦ㅰࡼࡗ࡚୰㙐ࡢỈ㓟⬡⫫㓟ኚࡋࠊẟ⌫ ẟᖿࠊ≉࣓ࣛࢽࣥ㢛⢏Ꮡᅾࡍࡿࠊࡑࡋ࡚ ALA ࡢ㓟௦ㅰ≀ࡣ ࢫࣇࣥࢦࢻ࡞ࡢࡁ࡞⬡㉁ศᏊࡢᵓᡂᡂศ㸦Ỉ㓟 C10 ⬡⫫㓟㸧 ࡋ࡚Ꮡᅾࡍࡿྍ⬟ᛶࢆ♧ࡋࡓࠋ ࡇࡢ௦ㅰ≀ࡣఱ≉ู࡞ᙺࡀ࠶ࡿࡢࡔࢁ࠺ࠋ ẟ⌫ෆࡢ࣓ࣛࣀࢧࢺ࠶ࡿ࣓ࣛࣀࢯ࣮࣒ෆ࡛ࠊࢳࣟࢩࢼ࣮ࢮࡢാࡁ
61 / 106 ࡼࡗ࡚ࢳࣟࢩࣥࡽ࣓ࣛࢽࣥⰍ⣲ࡀྜᡂࡉࢀࡿࠋᮍ⇍࡞ᵓ㐀ࡢ࣓ࣛࣀ ࢯ࣮࣒ࡢ㦵᱁࡞ࡿࢱࣥࣃࢡ㉁࣓ࣛࢽࣥ Ⰽ⣲ࡀỿ╔ࡋ࡚࠸ࡁࠊ⬡㉁⭷ ࡀ࣓ࣛࣀࢯ࣮࣒ࢆそ࠸ࠊᑡ㔞ࡢ࣑ࢿࣛࣝࢆྲྀࡾ㎸ࡴ㐣⛬ࢆ⤒࡚࣓ࣛࣀࢯ ࣮࣒ࡣᡂ⇍ࡋࡓ㢛⢏ᵓ㐀ࢆᙧᡂࡋࠊゅᇦ⛣ືࡋ࡚࠸ࡃࠋ⬡㉁ࡣ㢛⢏ ෆ㒊ࡶᏑᅾࡋࠊᙉᅛ⤖ྜࡋ࡚࠸ࡿࠋ
ALA ࡀ β 㓟ࡉࢀ࡚⏕ࡌࡿ୰㛫య㸦C10:3㸦2-trans, 4-cis, 7-cis㸧㸧 ࡣࠊ᭦ࣔࣀ࢜࢟ࢩࢤࢼ࣮ࢮࡸࣞࢲࢡࢱ࣮ࢮ㸦hydrogenases㸧ࡼࡗ࡚ ௦ㅰࡉࢀ࡚࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁୰ࡢỈ㓟 C10 ⬡⫫㓟ࢆ⏕ࡌࡿ᥎
ᐹࡉࢀࡿࠋᐇ㝿ࠊࣄࢺẟ᰿ࡣ⬡⫫㓟 oxygenase ࡢάᛶࡀぢฟࡉࢀ࡚
࠸ࡿ [86]ࠋ୍᪉ࠊALA ࡢ㐣㓟≀ࡋ࡚ࡣ hydroxyl యࠊoxo యࡸ
epoxy య࡞ከᵝ࡞㐣㓟≀ࡀᏑᅾࡍࡿ [87] ࡼࡾࠊ㓟㓝⣲ࡼࡿ ᛂ௨እࠊఱࡽࡢ⌮⏤࡛Ⓨ⏕ࡋࡓάᛶ㓟⣲ࡢࣛࢪ࢝ࣝᛂࡼࡗ ࡚㐣㓟≀ࡀ⏕ᡂࡍࡿ⪃࠼ࡽࢀࡿࠋᐇ㝿ࠊ࣓ࣛࣀࢧࢺࡢ࣓ࣛࢽࣥ⏕ ྜᡂ㐣⛬࡛ࡣࢳࣟࢩࢼ࣮ࢮࡼࡿࢳࣟࢩࣥࡢ㓟ࣄࢻࣟ࢟ࢩࣛࢪ࢝ࣝ ࡢᵝ࡞άᛶ㓟⣲✀ࡢⓎ⏕ࡼࡗ࡚⭷⬡㉁ࡢ㐣㓟ࡀ㉳ࡁࡿࡀࡼࡃ▱ࡽ ࢀ࡚࠸ࡿࠋࡇࢀࡼࡗ࡚ẟ⌫ࡸ⓶ࡢ࣓ࣛࣀࢧࢺ୰Ỉ㓟⬡⫫㓟ࡢ ⏕ᡂࡀ㉳ࡇࡿࡢࡶࡋࢀ࡞࠸ࠋ 㐟㞳ࣜࣀ࣮ࣝ㓟㸦C18:2n-6㸧ࡀࣘࣅ࢟ࢳࣥ㸫ࣉࣟࢸࢯ࣮࣒⤒㊰࡛ࢳ ࣟࢩࢼ࣮ࢮࡢศゎࢆຍ㏿ࡍࡿࡀሗ࿌ࡉࢀࡓ [88]ࠋࡲࡓࠊ᳜≀㸦Corchori㸧 ࡢⴥྵࡲࢀࡿỈ㓟⬡⫫㓟ࡀ࣏ࢫࢺࢦࣝࢪయ୰ࡢࢳࣟࢩࢼ࣮ࢮῶᑡࢆ ㄏ ᑟ ࡍ ࡿ ࡀ ሗ ࿌ ࡉ ࢀ ࡓ [89] ࠋ ࡑ ࢀ ࡽ ࡢ Ỉ 㓟 ⬡ ⫫ 㓟 ࡢ ୍ ࡘ ࡣ
16-Hydroxy-9-oxo-10E,12E,14E-octadecatrienoic acid㸦 Corchorifatty acid B㸧࡛࠶ࡾࠊn-3 㔜⤖ྜࢆࡶࡘ C18 ࡢ⬡⫫㓟ࡀỈ㓟ࡉࢀࡓ ALA ࡢ㓟௦ㅰ≀ࡢྍ⬟ᛶࡀ࠶ࡿࠋస⏝ᶵᵓࡣᮍ▱࡛࠶ࡿࡶࡢࡢࠊࡇࢀ
62 / 106 ࡽࡢ◊✲ࡣఱࡽࡢ⬡⫫㓟ࡀ࣓ࣛࣀࢯ࣮࣒⏕ྜᡂࢆไᚚࡍࡿྍ⬟ᛶࢆ♧ ၀ࡋ࡚࠸ࡿࠋ ᮏ◊✲ࡼࡾࠊせ࡞ ᚲ㡲⬡⫫㓟࡛࠶ࡿ ALA ⏤᮶ࡢ୰㙐Ỉ㓟⬡⫫㓟 㸦3, 6, 8-Ỉ㓟ࢹ࢝ࣥ㓟㸧ࡀ࣓ࣛࣀࢯ࣮࣒Ꮡᅾࡋࠊ㢮⦕⬡⫫㓟ࡀẟ⌫ ࠶ࡿ᥎ ࡉࢀࡓࠋࡇࢀࡽࡢ ALA ⏤᮶㓟௦ㅰ≀ࡣ࣓ࣛࣀࢯ࣮࣒ࡢ ྜᡂࠊ㍺㏦ࠊ⥔ᣢ࡞ࡢไᚚ࠾࠸࡚㔜せ࡞ᙺࢆᯝࡓࡍࡢ ࡛ࡣ࡞࠸ ⪃࠼࡚࠸ࡿࠋ
63 / 106
㸯㸫㸶㸬⤖ㄽ
ࣄࢺẟ㧥୰ࡢ⬡㉁ࡢศᕸࠊᵓ㐀ࠊ௦ㅰ≀ ࡘ࠸࡚◊✲ࡋࠊ୰࡛ࡶ≉ᚩ ⓗ࡞⬡㉁ࡘ࠸࡚ࡑࡢᙺࢆ⪃ᐹࡋࡓࠋ GlcNAc ࢆྵࡴఱࡽࡢࢫࢸࣜࣝࢢࣜࢥࢩࢻᵝ⬡㉁㢮㸦SGL㸧ࡢᑡ࡞ ࡃࡶ୍㒊ࡣẟᖿࡢ ࣮࢟ࣗࢸࢡࣝࢥࣝࢸࢵࢡࢫࡢ⏺㠃ศᕸࡋ࡚࠸ ࡿࠋࡑࡢ㇏ᐩ࡞Ỉ⣲⤖ྜࡢᐤ࡛࣮࢟ࣗࢸࢡࣝࢥࣝࢸࢵࢡࢫࡢ᥋╔ ᛶࢆ㧗ࡵࡿᙺࢆᯝࡓࡋ࡚࠸ࡿ ᥎ ࡋࡓࠋ ᚲ㡲⬡⫫㓟 ALA ࡢ㓟௦ㅰ≀᥎ ࡉࢀࡿ୰㙐ࡢỈ㓟⬡⫫㓟ࡣ㐟 㞳ᙧࡲࡓࡣࡁ࡞⬡㉁ࡢᵓ㐀ࡢ୍㒊ࡋ࡚ẟ⌫ࡸ࣓ࣛࣀࢯ࣮࣒Ꮡᅾࡍ ࡿࠋALA ࡢ㓟௦ㅰ≀ࡣ࣓ࣛࣀࢯ࣮࣒⤖ྜ⬡㉁ࡢ୍㒊ࡋ࡚ࠊ࣓ࣛࣀࢯ ࣮࣒ࡢ⏕ྜᡂ㐣⛬㛵ࢃࡗ࡚࠸ࡿࡢ࡛ࡣ࡞࠸⪃࠼ࡽࢀࡿࠋ ⏕య⥔ᣢྍḞ࡞≀㉁࡛࠶ࡿࡶ㛵ࢃࡽࡎࠊᚲ㡲⬡⫫㓟ࡢ ࣄࢺయෆ ືែࡣᚑ᮶ࢇᮍゎ᫂࡞ࡲࡲ࡛࠶ࡗࡓࠋࡋࡋ ࠊᮏ◊✲࠾࠸࡚⬡ ㉁௦ㅰࡢሙࡋ࡚ẟ㧥↔Ⅼࢆᙜ࡚ࠊ ࡑࡢయෆືែࡢࣈࣛࢵࢡ࣎ࢵࢡࢫ ࢆ㒊ศⓗ࡛ࡶ㛤ࡃ⮳ࡗࡓ⪃࠼ࡿࠋᮏ◊✲ࡣㄽᩥ "Distribution of Glycolipid and Unsaturated Fatty Acids in Human Hair" ࡋ࡚Ꮫ⾡ㄅ Lipids ᥖ㍕ࡉࢀࡓ㸦Takahashi T, Yoshida S (2014) 49:905-917㸧ࠋᮏㄽᩥ୰ࡢ Figure 8ࠊ10-13ࠊ15ࠊ 16ࠊ19-21 ࡣ Springer Science and Business Media ࡢࡈཌពࡼࡾチ ྍࢆᚓ࡚㌿㍕ࡋࡓࡶࡢ࡛࠶ࡿࠋ
64 / 106
➨㸰❶ ẟ㧥≀ᛶ◊✲
65 / 106
㸰㸫㸯㸬⫼ᬒ
ẟ㧥ࡣእⓗ⎔ቃᖖ᥋ࡋ࡚࠸ࡿࠋኴ㝧ගࠊỈ㸦㞵ࠊධᾎࠊࣉ࣮ࣝ㸧 ࡣࡶࡼࡾࠊὙ㧥ࠊࣈࣛࢵࢩࣥࢢࠊࢱ࢜ࣝࢻࣛࠊࣈ࣮ࣟࡸᐷලࡢᦶ ᧿࡞ẖ᪥ࡢ⩦័ⓗ⾜ືࡼࡿ่⃭ࠊ᭦ࡣ࣮࣊࢝ࣛࡸࣃ࣮࣐ࠊ࣊ ࣟࣥ࡞ࡢ㐣㓞࡞Ꮫฎ⌮ࠊ⇕ฎ⌮ࠊ≀⌮ⓗ่⃭ࡉࢀࡿᶵࡀ ࣄࢺࡢჾᐁࡢ୰࡛ࡣ⩌ࢆᢤ࠸࡚ከ࠸ࠋࡇࢀࡽࡢ่⃭ࡼࡗ࡚ᵓ㐀ࡸᡂศ ࡢ◚ቯ࣭ὶฟࡀ⏕ࡌࠊࡑࡢ⤖ᯝࡋ࡚ᐇឤࡉࢀࡿࢲ࣓࣮ࢪࡋ࡚ࡣࢦ࣡ ࡘࡁࠊẟὶࢀࡢࢀࠊࢶࣖࡢపୗࠊ⬺Ⰽࠊᯞẟ࣭ษࢀẟ࡞ᯛᣲᬤࡀ ࡞࠸ [58, 90-112]ࠋ ẟ㧥ࡢ⤌⧊ࡢ୰࡛ࡶ≉ࠊ᪥ᖖⓗ࡞่⃭ࢆ┿ࡗඛཷࡅࡿࡢࡣ⾲ᒙ⤌ ⧊ࡢ࣮࢟ࣗࢸࢡ࡛ࣝ࠶ࡾࠊᚎࠎᦶ⪖ࡋ࡚࠸ࡃࠋࡑࡢࡓࡵࠊṤࡢሙ ྜࠊ᰿ඖ㒊ศẚ㍑ࡍࡿẟඛ㒊ศࡢ࣮࢟ࣗࢸࢡࣝࡢᯛᩘࡣᑡ࡞ࡃࠊ ᙧ≧ࡀࢀ࡚࠸ࡿࠋ ➹ ⪅ ࡽ ࡣ 2006 ᖺ࣮࢟ࣗࢸࢡࣝࡢ ᦆയࡀึࡵⓎ⏕ࡍ ࡿ㒊ࡣ ࣮࢟ࣗࢸࢡࣝ⣽⬊㛫ࡢ CMC ࢚ࣥࢻ࣮࢟ࣗࢸࢡࣝࡢ 2 ⟠ᡤ࡛࠶ ࡾ ࠊ ࡑ ࢀ ࡒ ࢀ ࡢ Ⓨ ⏕ 㢖 ᗘ ࡀ ே ✀ ࡼ ࡗ ࡚ ᫂ ☜ ␗ ࡞ ࡿ ࢆ ሗ ࿌ ࡋ ࡓ [113]ࠋ20㹼40 ௦ࡢ᪥ᮏேዪᛶ Caucasian㸦࣓ࣜ࢝ࠊࢻࢶ㸧ዪᛶ ࡢẟ㧥㈇Ⲵࢆ࠼ ࡿࠊ๓⪅ࡣ CMCࠊᚋ⪅ࡣ࢚ࣥࢻ࣮࢟ࣗࢸࢡࣝ ࡀࡼࡾቯࢀࡸࡍ࠸ഴྥ࠶ࡗࡓࠋࡲࡓࠊ࢚ࣥࢻ࣮࢟ࣗࢸࢡࣝࡢ◳ᗘࡣ ᪥ᮏேẟࡢ᪉ࡀ㧗࠸࠸࠺⤖ᯝࢆᚓࡓ ࠋCMC ࢚ࣥࢻ࣮࢟ࣗࢸࢡࣝ ࡢ┦ᑐⓗ࡞ᙉᗘࣂࣛࣥࢫࡼࡗ࡚ࢲ࣓࣮ࢪࢱࣉࡀỴࡲࡿⅭࠊ᪥ᮏேẟ ࡛ࡣ CMC ࡢᦆቯࡀඃඛⓗ㉳ࡁࡿ⪃࠼ࡓࠋ66 / 106
㸰㸫㸰㸬┠ⓗ
ᖺ㱋ࡶ㧥㉁ࡀኚࡍࡿࡣᗈࡃᐇឤࡉࢀ࡚࠸ࡿ ࠋᮏ◊✲࡛ࡣ࢟ ࣮ࣗࢸࢡࣝࡢ่⃭⪏ᛶࠊᦆയᣲືࡢᖺ㱋౫Ꮡኚὀ┠ࡋࠊࡑࢀࡀẟ 㧥ࡢ≉ᛶཬࡰࡍᙳ㡪ࡢゎ᫂ࢆ┠ⓗࡋࡓࠋ
