http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1829.pdf

2010B1829                          BL40XU

ᗈゅ X ⥺ᅇᢡ࠾ࡼࡧᑠゅ X ⥺ᩓ஘ἲ࡟ࡼࡿ ppm ࣮࢜ࢲ࣮ࡢࣇࢵ⣲ࢆྵࡴ࢝ࣝࢩ࣒࢘ྵ᭷㣗ရ࡟ࡼࡿ෌▼⅊໬ࡀṑ࢚ࢼ࣓ࣝ㉁ࡢ
ࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ⤖ᬗ࡟ཬࡰࡍᵓ㐀ࡢኚ໬ࡢゎᯒ
Analysis by Wide-angle X-ray Diffraction and Small-angle X-ray Scattering
Methods for the Structural Change of Hydroxyapatite Crystallites inEnamel by the Reminalization with Calcium Containing Food with
ppm-order Fluoride⏣୰ ᬛᏊ a, ᑠᯘ㝯Ⴙ a, ⁪஭ ᐶ a, 㔩㜰 ᐶ a, ኴ⏣ ᪼ b, ඵᮌ ┤ே b
Tomoko Tanakaa, Takatsugu Kobayashia, Hiroshi Takiia, Hiroshi Kamasakaa, Noboru Ohtab, Naoto YagibaỤᓮࢢࣜࢥ㻔ᰴ㻕, b㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮a
Ezaki Glico Co., Ltd., bJASRIᡃࠎࡣࠊࡇࢀࡲ࡛ࡢ◊✲࠿ࡽึᮇ࠺⼃㻔ึᮇࡴࡋṑ㻕࡟࠾ࡅࡿ࢝ࣝࢩ࣒࢘࢖࢜ࣥࡢ෌⤖ᬗ໬ຠᯝࢆぢฟࡋ࡚ࡁࡓࠋࣇࢵ⣲ࢆే⏝ࡍࡿ࡜ࠊࡉࡽ࡟㧗࠸࠺⼃ண㜵ຠᯝࡀぢ㎸ࡲࢀࡿࡀࠊ෌⤖ᬗ໬࡟ཬࡰࡍຠᯝࡣᮍࡔゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊప⃰ᗘࡢࣇࢵ⣲࢖࢜ࣥࡀ◳⤌⧊࡛࠶ࡿṑ࢚ࢼ࣓ࣝ㉁⤖ᬗ࡟ᑐࡍࡿຠᯝࢆࠊᚤ⣽⤖ᬗࣞ࣋ࣝ࠿ࡽゎᯒࡋࡓࠋ⤖ᯝࠊᴟᚤ㔞ࡢࣇࢵ⣲࢖࢜ࣥࡢᏑᅾ࡛࢝ࣝࢩ࣒࢘࢖࢜ࣥ༢య࡜ࡣ␗࡞ࡿຠᯝࢆࡶࡓࡽࡍࡇ࡜ࡀุ᫂ࡋࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺࠊࣇࢵ⣲ࠊᗈゅ X ⥺ᅇᢡ⫼ᬒ࡜◊✲┠ⓗ㸸ᚑ᮶ࣇࢵ⣲ࡣࠊṑ⛉་⒪࡟࠾࠸࡚࠺⼃ண㜵ຠᯝࡀ㧗࠸࡜ࡉࢀࡿ⣲ᮦ࡛࠶ࡿ[1][2]ࠋࡑࡢά⏝ἲࡣ኱ࡲ࠿࡟ศࡅࡿ࡜ࠊ㧗⃰ᗘฎ⌮࡟ࡼࡿᒁᡤⓗᡭἲ࡜ప⃰ᗘ࡟ࡼࡿ඲㌟ⓗᡭἲࡢ 2 ✀㢮ࡀ࠶ࡿ[3]ࠋᒁᡤⓗᡭἲࡣࣉࣟࣇ࢙ࢵࢩࣙࢼࣝࢣ࢔ࡀ୺ὶ࡛࠶ࡿࠋ୍᪉ࠊప⃰ᗘ࡟ࡼࡿ඲㌟ⓗᡭἲࡣࠊᾏእ࡛ࡣỈ㐨Ỉ࡟ῧຍࡍࡿ࢛࣮࢘ࢱ࣮ࣇࣟࣜࢹ࣮ࢩࣙࣥ࡞࡝࡟௦⾲ࡉࢀࡿࠋࣇࢵ⣲࡟ࡼࡿṑ㉁ᙉ໬࡟ࡘ
࠸࡚ࡣࠊ࠶ࡿ⛬ᗘࢥࣥࢭࣥࢧࢫࡀᚓࡽࢀ࡚࠸ࡿࡀࠊ୺࡟ࣇࢵ⣲ྲྀࡾ㎸ࡳ࡟ࡼࡿࣇࢵ໬࢔ࣃࢱ࢖ࢺ࡬ࡢ⨨᥮ࡀࡶࡓࡽࡍ⪏㓟ᛶ࡞࡝ࡢ໬Ꮫⓗせᅉࡀ୺࡜ࡉࢀ࡚ࡁࡓࠋ୍᪉ࠊࣇࢵ⣲ࡀ࠶ࡿࡇ࡜࡟ࡼࡾࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ⤖ᬗࡢᡂ㛗ࡀಁ㐍ࡉࢀࡿ࡜࠸࠺♧၀ࡶ࠶ࡿࡶࡢࡢࠊᐇ㝿࡟⤖ᬗࡢ㉁ࡸᡂ㛗㔞࡟࡝ࡢࡼ࠺࡞ᙳ㡪ࢆཬࡰࡍ࠿ࡣ᫂ࡽ࠿࡛ࡣ࡞࠸ࠋࡲࡓ◊✲⪅ࡢ୰࡟ࡣࠊప⃰ᗘࡢࣇࢵ⣲࢖࢜ࣥࡢ෌▼⅊໬࣭ṑ㉁ቑᙉ࡟ᑐࡍࡿຠᯝ࡟ࡘ࠸࡚␲ၥどࡍࡿኌࡶ࠶ࡿࠋࡑࡢ⫼ᬒ࡟ࡣࠊప⃰ᗘࡢࣇࢵ⣲࢖࢜ࣥࡀṑ࢚ࢼ࣓ࣝ㉁࡟ᾐ㏱ࡋ࡚࢔ࣃࢱ࢖ࢺ⤖ᬗࡢ㓄ิࡸᙉᗘ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࢆ᳨
ドࡍࡿ㐺ᙜ࡞ᡭἲࡀᵓ⠏ࡉࢀ࡚࠸࡞࠿ࡗࡓࡇ࡜ࡀᣲࡆࡽࢀࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊࡇࢀࡲ࡛ࡢ◊✲ᡂᯝ࡟࠾࠸࡚ SPring-8 ࡢ㧗㍤ᗘ࣐࢖ࢡࣟ X ⥺ࢆ⏝࠸ࡓ X ⥺ᅇᢡἲ࡟ࡼࡾึᮇ࠺⼃ࡢᚤ⣽ᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡋࡓᡭἲ[4][5][6]ࢆά⏝ࡍࡿࡇ࡜࡛ࠊప⃰ᗘࡢࣇࢵ⣲࢖࢜ࣥࡀṑ࢚ࢼ࣓ࣝ㉁ࡢࣁ࢖ࢻ
ࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ⤖ᬗ࡟୚࠼ࡿຠᯝࢆ᳨ドࡍࡿࡇ࡜࡜ࡋࡓࠋ≉࡟ࠊึᮇ࠺⼃࠾ࡅࡿ࢝ࣝࢩ࣒࢘ࡢ
෌▼⅊໬ຠᯝ࡜ࡢ┦㐪࡟ࡘ࠸࡚✀ࠎࡢ࢝ࣝࢩ࣒࢘⣲ᮦࡢຠᯝ࡜ẚ㍑ࡋ࡞ࡀࡽ᳨ウࡋࡓࠋᐇ㦂㸸ṑࡢ⾲㠃ࢆ๐ࡗ࡚࢚ࢼ࣓ࣝ㠃ࢆฟࡋࠊ⬺⅊ฎ⌮࠾ࡼࡧ෌▼⅊໬ฎ⌮ࢆ⾜ࡗ࡚ࠊ1 ṑ∦ୖ࡟೺඲࣭
⬺⅊࣭෌▼⅊໬㒊ࢆసᡂࡋࡓࡶࡢࢆཌࡉ 150 μm ࡟ษࡾฟࡋࠊࢧࣥࣉࣝ࡜ࡋࡓࠋ෌▼⅊໬ฎ⌮࡟ࡣࠊ
⾲ 1 ࡟♧ࡍࡼ࠺࡞ၚᾮ⤌ᡂ࡟㏆࡙ࡅࡓ࣑ࢿࣛࣝ⁐ᾮࢆ POs-Ca+ࣇࢵ⣲ࠊPOs-Ca ࡛ㄪ〇ࡋࡓྛ෌▼⅊໬ฎ⌮ᾮ࡛཯ᛂࢆ⾜࠸ࠊࡑࡢຠᯝࢆẚ㍑ࡋࡓࠋヨᩱ࡟ࡣࠊ࢘ࢩṑ࠾ࡼࡧࣄࢺṑࢆ⏝࠸ࡓࠋ࢘ࢩ
ṑࡣᖺ㱋࠾ࡼࡧ㣗⏕άࡀẚ㍑ⓗᆒ୍࡛࠶ࡿࡇ࡜ࠊヨᩱᩘࡀᥞ࠼ࡸࡍ࠸ࡇ࡜࠿ࡽ㢖⏝ࡉࢀ࡚࠸ࡿࠋ
ࣄࢺṑࡣࠊᖺ㱋ࠊ㣗⏕άࡢࡤࡽࡘࡁ࠿ࡽࠊᆒ୍࡞ヨᩱࢆ୍ᐃᩘᥞ࠼ࡿࡇ࡜ࡀࡁࢃࡵ࡚ᅔ㞴࡛࠶ࡿࡇ࡜࠿ࡽࠊᮏ◊✲࡛ࡣணഛⓗヨ㦂࡜ࡋ࡚ᩘࢧࣥࣉࣝࢆ᳨ウࡍࡿࡶࡢ࡜ࡋࡓࠋ

ྛヨᩱࡣୗグࡢࡼ࠺࡟ㄪᩚࡋࡓࠋ
࣭࢘ࢩ࢚ࢼ࣓ࣝ㉁ⷧ∦ࢧࣥࣉࣝ㻔ཌࡉ 150 μ㹫, ⾲㠃✚ 5 mm × 10 mm㻕
࣭ࣄࢺ࢚ࢼ࣓ࣝ㉁ⷧ∦ࢧࣥࣉࣝ㻔ཌࡉ 150 μ㹫, ⾲㠃✚ 5 mm × 10 mm㻕
ୖグࡢヨᩱ࡟ࡘ࠸࡚ࠊ࢚ࢼ࣓ࣝ㉁-㇟∳㉁᪉ྥ㻔ṑࡢ῝ࡉ᪉ྥ㻕࡟ᑐࡋ࡚ᆶ┤࡟ࣅ࣮࣒ࢆᙜ࡚ࡿ
ࡼ࠺࡟ࣅ࣮࣒ࣛ࢖ࣥࡢ 2 ḟඖ࡟⛣ືྍ⬟࡞ヨᩱࢫࢸ࣮ࢪ࡟ࢭࢵࢺࡋࠊX ⥺ࢆ↷ᑕࡋࡓࠋ ᐃࡣࠊ6μm ⛬ᗘࡢ኱ࡁࡉࡢ X ⥺ࣅ࣮࣒࡜࡞ࡿࡼ࠺࡟ࠊࣆ࣮ࣥ࣍ࣝࢆ㏻ࡋ࡚ㄪᩚࡋࡓ 15 keV ๓ᚋࡢ X ⥺ࢆ↷ᑕࡋࠊᅇᢡീࢆᚓࡓࠋࡇࢀࢆ 60 ࢧࣥࣉࣝ࡟ࡘ࠸࡚ࠊ࢚ࢼ࣓ࣝ⾲㠃࠿ࡽ῝㒊࡟ྥ࠿ࡗ࡚ 5 μm ࡈ࡜࡟῝ࡉ 200 μm ࡲ࡛⾜ࡗࡓࠋᚓࡽࢀࡓ X ⥺ᅇᢡࢹ࣮ࢱ࡟ࡘ࠸࡚ࡣࠊHAp ⤖ᬗࡢ c ㍈ࡢ⣽࠿࡞㐪࠸࡟ᙳ㡪ࡉࢀ࡟ࡃ࠸ HAp ⏤᮶ࡢ㻌 㻔100㻕㻌 ࡢ཯ᑕ࡟ࡘ࠸࡚ᙉᗘ✚ศࢆ⾜࠸ࠊ೺඲㒊ࡢᙉᗘ࡛┦ᑐ್໬ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊྛ ᐃⅬ࡟࠾ࡅࡿ HAp ⤖ᬗྵ᭷㔞ࢆ⟬ฟࡋࡓ㻔⤖ᬗࣉࣟࣇ࢓࢖࣭ࣝᅗ 1-A ཧ↷㻕ࠋ⤖ᬗࡢࣉࣟࣇ࢓࢖ࣝ࠿ࡽᅇ᚟⋡ࢆィ⟬ࡋࡓࠋ⾲ 1㸬ྛ✀෌▼⅊໬ฎ⌮ᾮ⤌ᡂCa 㻔POs-Ca㻕
KH2PO4F 㻔Tea extract㻕
HEPES
pHTotal

1.2

ձ
6 mM
3.6 mM
1 ppm
20 mM
6.5
100 mLղ
6 mM
3.6 mM
0 ppm
20 mM
6.5100 mL෌⤖ᬗ໬㒊఩

HAp⤖ᬗ㔞1.00.80.6ึᮇ䜐䛧ṑ㒊఩

0.4
0.2
0.0050100150200䜶䝘䝯䝹⾲㠃䛛䜙䛾῝䛥 (Pm)ᅗ 1-A㸬ᗈゅ X ⥺ᅇᢡゎᯒ࡟ࡼࡿ࢔ࣃࢱ࢖ࢺ⤖ᬗኚ໬㔞ࣉࣟࣇ࢓࢖ࣝ

100(Mineral loss(Vol%.ȝm)෌⤖ᬗ໬㒊఩
8060ึᮇ䜐䛧ṑ㒊఩

40
20
0050

100150200䜶䝘䝯䝹⾲㠃䛛䜙䛾῝䛥 (Pm)

ᅗ 1-B㸬X ⥺㏱㐣ἲ࡟ࡼࡿ࣑ࢿࣛࣝኚ໬㔞ࣉࣟࣇ࢓࢖ࣝ

⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸࠙฼⏝᪉ἲ࠾ࡼࡧ฼⏝ࡢ⤖ᯝᚓࡽࢀࡓ୺࡞ࢹ࣮ࢱࠚ
X ⥺࣐࢖ࢡࣟࣅ࣮࣒ࢆ⏝࠸ࡓ WAXRD ࡢゎᯒ࠿ࡽ෌▼⅊໬ࡉࢀࡓ㒊఩ࡢᅇ᚟ࡢ୍㒊ࡣᑡ࡞ࡃ࡜
ࡶࠊPOs-Ca+ࣇࢵ⣲㻔F㻕࠾ࡼࡧ POs-Ca ࡛෌▼⅊໬ࡋࡓ࠸ࡎࢀࡢṑࡶ೺඲㒊ࡢ࢚ࢼ࣓ࣝ㉁࡜ྠࡌ㓄ྥᛶࢆ᭷ࡋࡓࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ⤖ᬗࡢᅇ᚟ࡀほࡽࢀࡓ㻔ᅗ 1-A㻕ࠋࡲࡓ POs-Ca㸩F ࡢ࡯࠺ࡀPOs-Ca ༢⊂ฎ⌮ࡼࡾࡶ෌⤖ᬗ໬ࢆࡼࡾಁ㐍ࡍࡿഴྥࡀ♧ࡉࢀࡓࠋࡇࡢ⤖ᯝࡣࠊX ⥺㏱㐣ἲ࡟ࡼࡿ෌▼⅊໬ࡢホ౯⤖ᯝ࡜ྠᵝࡢഴྥ࡛࠶ࡗࡓ㻔ᅗ 1-B㻕ࠋࡇࡢࡇ࡜࠿ࡽࠊᴟᚤ㔞ࡢ F ῧຍࢆ⾜࠺࡜ࠊ
POs-Ca ࡜┦஌ⓗ࡟෌▼⅊໬࣭෌⤖ᬗ໬ຠᯝࢆⓎ᥹ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ୍᪉௒ᅇࡢ᳨ド࡛ࡣࠊࣄࢺṑ࡟࠾ࡅࡿಶయᕪࡀ኱ࡁࡃࠊࣄࢺṑ࡛ࡢ᫂░࡞ᡂᯝࢆᚓࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋࡲࡓ௒ᅇࡢ᳨ド࡛ࡣࣇࢵ⣲ࡢṑ࡬ࡢᾐ㏱ᗘࠊྲྀࡾ㎸ࡳᙧែ㻔ࣇࢵ໬࢔ࣃࢱ࢖ࢺࠊࣇࢵ໬࢝ࣝࢩ࣒࢘ࠊࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺࡢ࠸ࡎࢀࡀᏑᅾࡍࡿࡢ࠿➼㻕࡟ࡘ࠸࡚ホ౯ࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ௒ᚋࠊ௚ࡢゎᯒἲ࡞࡝ࢆά⏝ࡋከ㠃ⓗ࡟ホ౯ࡋ࡚ࣇࢵ⣲ࡢྲྀࡾ㎸ࡳᙧែࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࠊࣄࢺṑ࡛ࠊ࡛ࡁࡿࡔࡅࣂࣛࢶ࢟ࢆᨵၿࡍࡿ᪉ἲ➼࡟ࡘ࠸᳨࡚ウࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋཧ⪃ᩥ⊩㸸
[1] Dean H. T., et al., Domestic water and dental caries. Additional studies of the relation of fluoride
domestic waters to dental caries experience in 4,425 while children, aged 12 to 14 years, of 13 cities in
4 States. Pub. Health Rep., 57, 1155-1179, 㻔1942㻕.
[2] Dean H. T. Chronic endemic dental Fluorosis 㻔Mottled Enamel㻕, J. Am. Med. Assoc., 107, 1269-1272,
㻔1936㻕㻚
[3] ࣇࢵ໬≀⮫ᗋᛂ⏝ࡢࢧ࢖࢚ࣥࢫ┘ಟ㧗ỤὪ⩏▴Ọᮎ᭩ᗑᮾி, 101, 㻔2002㻕.
[4] Yagi N., Ohta N., Matsuo T., Tanaka T., Terada Y., Kamasaka H., To-o K., Kometani T., Kuriki T.
Evaluation of enamel crystallites in subsurface legion by microbeam X-ray diffraction. J. Synchrotoron
Radiat., 16, 398-404, 㻔2009㻕.
[5] Tanaka M. et al., Effect of chewing gum containing Phosphoryl Oligosaccharides of Calcium㻌㻔POs-Ca㻕on remineralization and hydroxyapatite crystallites of enamel subsurface lesions in situ. ᪥ᮏṑ⛉ಖᏑᏛ఍ㄅ, 52, 534-542, 㻔2009㻕.
[6] Tanaka T., Yagi N., Ohta N., Matsuo T., Terada Y., Kamasaka H., To-o K., Kometani T., Kuriki T.
Evaluation of the distribution and orientation of remineralized enamel crystallites in subsurface lesionby X-ray diffraction. Caries Res., 44, 253-259, 㻔2010㻕㻚