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JPS6139314B2 - - Google Patents
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JPS6139314B2 - - Google Patents

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Publication number
JPS6139314B2
JPS6139314B2 JP10889283A JP10889283A JPS6139314B2 JP S6139314 B2 JPS6139314 B2 JP S6139314B2 JP 10889283 A JP10889283 A JP 10889283A JP 10889283 A JP10889283 A JP 10889283A JP S6139314 B2 JPS6139314 B2 JP S6139314B2
Authority
JP
Japan
Prior art keywords
acid
phosphate
present
hpo
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP10889283A
Other languages
Japanese (ja)
Other versions
JPS601188A (en
Inventor
Hideki Kadoma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KAGAKU GIJUTSUCHO MUKIZAISHITSU KENKYUSHOCHO
Original Assignee
KAGAKU GIJUTSUCHO MUKIZAISHITSU KENKYUSHOCHO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KAGAKU GIJUTSUCHO MUKIZAISHITSU KENKYUSHOCHO filed Critical KAGAKU GIJUTSUCHO MUKIZAISHITSU KENKYUSHOCHO
Priority to JP10889283A priority Critical patent/JPS601188A/en
Publication of JPS601188A publication Critical patent/JPS601188A/en
Publication of JPS6139314B2 publication Critical patent/JPS6139314B2/ja
Granted legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は一般式 Ca8(PO44(HPO42-Z・(Co2oC2O4Z
mH2O (ただし、式中Zは0より大きく1以下の数、
nは1より大きく6以下の整数、mは4〜8の数
を表わす)で示される新規な複合化合物(以下、
本発明の複合化合物という)およびその製造法に
関する。 従来、燐酸カルシウムと有機質との相互作用に
ついては、主に生体内での骨歯・結石の生理を理
解するため、また、燐酸カルシウムの有機質に対
するクロマトグラフイツクな性質を調べる材料と
して研究されてきたが、燐酸八カルシウムがその
結晶構造内に有機質を取り込んだ複合化合物は知
られていない。また一般に分子またはイオンサイ
ズが大きく、かつ立体構造を持つ有機質が、いわ
ゆる層状またはかご状構造の化合物に分類されな
い燐酸八カルシウム構造内に取り込まれる可能性
は予想されていなかつた。 本発明の目的は従来の表面吸着型の燐酸カルシ
ウムと有機質のものとは異なる構造内収容型の新
規な燐酸八カルシウムと有機酸との複合化合物を
提供するにある。 本発明者は前記目的を達成すべく研究の結果、
α―燐酸三カルシウム(α―Ca3(PO42)を、一
般式Co2oC2O -(ただし、nは1より大きく6
以下の整数を表わす)で示される有機酸イオンの
共存下、PH5〜7の下で加水分解したところ、該
有機酸イオンを燐酸八カルシウムの構造内に取り
込んだ本発明の複合化合物が得られることを知見
し得た。この知見に基いて本発明を完成した。 本発明の複合化合物が燐酸八カルシウムの構造
内に有機酸イオンが取り込んでいることは、次の
ことによつて証明し得られる。 1 燐酸八カルシウムの構造の底面間隔が拡がつ
ていること。この測定結果は次の表1の通りで
ある。
The present invention is based on the general formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-Z・(C o H 2o C 2 O 4 ) Z
mH 2 O (where Z is a number greater than 0 and less than or equal to 1,
A novel complex compound (hereinafter referred to as
The present invention relates to a composite compound of the present invention) and a method for producing the same. Until now, the interaction between calcium phosphate and organic matter has been studied mainly to understand the physiology of bones, teeth and calculus in vivo, and as a material for investigating the chromatographic properties of calcium phosphate with respect to organic matter. However, there are no known complex compounds in which octacalcium phosphate incorporates organic matter into its crystal structure. Furthermore, it was not anticipated that organic substances, which generally have a large molecular or ion size and a three-dimensional structure, could be incorporated into the octacalcium phosphate structure, which is not classified as a compound with a so-called layered or cage structure. An object of the present invention is to provide a novel composite compound of octacalcium phosphate and an organic acid, which is a structurally encapsulated type that is different from the conventional surface-adsorbed calcium phosphate and organic compound. As a result of research to achieve the above object, the present inventor has
α-Tricalcium phosphate (α-Ca 3 (PO 4 ) 2 ) is expressed by the general formula C o H 2o C 2 O 2 4 - (where n is greater than 1 and 6
When hydrolyzed at pH 5 to 7 in the presence of an organic acid ion represented by the following integer, a composite compound of the present invention in which the organic acid ion is incorporated into the structure of octacalcium phosphate is obtained. I was able to find out. The present invention was completed based on this knowledge. The fact that the composite compound of the present invention incorporates organic acid ions into the structure of octacalcium phosphate can be demonstrated by the following. 1. The basal spacing of the structure of octacalcium phosphate is expanding. The measurement results are shown in Table 1 below.

【表】 2 有機酸イオンがHPO -イオンと置換してい
ることは、燐酸八カルシウム(Ca8(PO44
(HPO42・5H2O)のCa/Pモル比が1.33より
増大していることによつて確められる。すなわ
ち、結晶構造を保つたままで、Ca/P比を増
大させるためには、燐酸イオンの溶出を考える
のが自然であり、また同時に電気的中性条件に
よつて有機酸イオンが取り入れられたものと考
える。 本発明の複合化合物の赤外線吸収スペクトルを
示すと第3図の通りである。またその底面間隔の
加熱による変化ならびに加熱による重量変化を示
すと、それぞれ、第2図および第1図の通りであ
る。なお、加熱による重量変化は、静止空気中
で、試料20.0mgを昇温10℃/分で加熱してその重
量の減少を測定した結果である。 本発明の複合化合物は、α―リン酸三カルシウ
ムを該当有機酸イオン含有水溶液に懸濁させ、PH
を5〜7の範囲で加水分解することにより製造さ
れる。 前記製造法において、α―燐酸三カルシウムに
代え、燐酸八カルシウム粉末を使用すると、構造
内収容型の複合化合物は得られない。 また、PHは5〜7の範囲であることが必要であ
る。PHが5より小さいと燐酸―水素カルシウム
(CaHPO4・2H2O)が生成し、7を超えると水酸
アパタイトが生成して構造内収容型の複合化合物
は得られない。 一般式Co2oC2O -イオンの有機酸としては、
nが1より大きく6以下の整数の有機酸であり、
例えば、マロン酸,コハク酸,グルタン酸,アジ
ピン酸,ピメリン酸,スベリン酸が挙げられる。
nが0のシユウ酸では不溶性シユウ酸カルシウム
を生成し、シユウ酸イオンと燐酸八カルシウムと
の複合は生じない。 また、nが7以上の有機酸では、これら自身あ
るいはこれらのカルシウム塩が難溶性のために、
燐酸八カルシウムとの構造内収容型複合化は容易
ではなくなり、不溶性の有機酸カルシウムまたは
単に燐酸八カルシウムを優先的に生成するように
なる。 本発明の複合化合物は、燐酸八カルシウムへの
有機化合物の複合化の中間原料、生体骨歯・石灰
化の生理研究の試料として使用し得られる。ま
た、他の粉末の防結および流動調整剤、蛋白質ま
たは核酸類のクロマトグラフイー吸着体、プラス
チツクス用フイラー、イオン交換体などに使用し
得られる。 以上のように、本発明によると、新規な燐酸八
カルシウムの構造内に有機酸イオンを取り込んだ
複合化合物およびその製造法を提供し得た優れた
効果を奏し得られる。 実施例 1 α―燐酸三カルシウム粉末1gを、アンモニア
水でPH6.4に調製した0.25モル濃度のマロン酸水
溶液50ml中に投入し、40℃で3時間保持した後、
固相を過・水洗し、40℃で乾燥した。その反応
率は45%であつた。固相分のCa/Pモル比は
1.47で、その構造の底面間隔は20.2Åであり、そ
の化学組成はCa8(PO44(HPO41.58
(CH2C2O40.42・5.3H2O相当であつた。 実施例 2 実施例1において、PH6.4をPH6.0にし、マロン
酸に代えコハク酸を使用した。その反応率は100
%であつた。固相分のCa/Pモル比は1.58で、
その構造の底面間隔は21.4Åであり、その化学組
成はCa8(PO44(HPO41.06(C2H4C2O40.94
5.9H2O相当であつた。 実施例 3 実施例2においてコハク酸に代えグルタル酸を
使用した。その反応率は60%であつた。固相分の
Ca/Pモル比は1.45で、その構造の底面間隔は
22.3Åであり、その化学組成はCa8(PO44
(HPO41.65(C3H6C2O40.35・5H2O相当であつ
た。 実施例 4 実施例2において、コハク酸に代えアジピン酸
を使用した。その反応率は100%であつた。固相
分のCa/Pモル比は1.44で、その構造の底面間
隔は23.6Åであり、その化学組成はCa8(PO44
(HPO41.55(C4H8C2O4045・6.6H2O相当であ
つた。 実施例 5 実施例2において、コハク酸に代えピメリン酸
を使用した。その反応率は80%であつた。固相分
のCa/Pモル比は1.41で、その構造の底面間隔
は25.1Åであり、その化学組成はCa8(PO44
(HPO41.78(C5H10C2O40.22・5.0H2O相当であ
つた。 実施例 6 実施例2において、コハク酸に代えスペリン酸
を使用した。その反応率は70%であつた。固相分
のCa/Pモル比は1.55で、その構造の底面間隔
は26.1Åであり、その化学組成はCa8(PO44
(HPO41.08(C6H12C2O40.92・7.6H2O相当であ
つた。
[Table] 2 The fact that organic acid ions are substituted with HPO 2 4 -ions means that octacalcium phosphate (Ca 8 (PO 4 ) 4
This is confirmed by the Ca/P molar ratio of (HPO 4 ) 2 ·5H 2 O) increasing from 1.33. In other words, in order to increase the Ca/P ratio while maintaining the crystal structure, it is natural to consider elution of phosphate ions, and at the same time, organic acid ions are introduced under electrically neutral conditions. I think so. FIG. 3 shows the infrared absorption spectrum of the composite compound of the present invention. Further, the changes in the distance between the bottom surfaces due to heating and the changes in weight due to heating are shown in FIGS. 2 and 1, respectively. Note that the weight change due to heating is the result of heating 20.0 mg of a sample in still air at a heating rate of 10° C./min and measuring the decrease in weight. The composite compound of the present invention is produced by suspending α-tricalcium phosphate in an aqueous solution containing the corresponding organic acid ion, and
It is produced by hydrolyzing in the range of 5 to 7. In the above production method, if octacalcium phosphate powder is used instead of α-tricalcium phosphate, a structurally encapsulated composite compound cannot be obtained. Further, the pH needs to be in the range of 5 to 7. If the pH is less than 5, calcium phosphate-hydrogen (CaHPO 4 .2H 2 O) is produced, and if it exceeds 7, hydroxyapatite is produced, making it impossible to obtain a structurally contained composite compound. Organic acids with the general formula C o H 2o C 2 O 2 4 -ion include:
an organic acid where n is an integer greater than 1 and less than or equal to 6;
Examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid.
Oxalic acid in which n is 0 produces insoluble calcium oxalate, and no complexing of oxalate ion and octacalcium phosphate occurs. In addition, organic acids with n of 7 or more are difficult to dissolve because they themselves or their calcium salts are poorly soluble.
Intramural complexation with octacalcium phosphate is no longer easy, and insoluble organic calcium acids or simply octacalcium phosphate are preferentially produced. The composite compound of the present invention can be used as an intermediate raw material for conjugating an organic compound to octacalcium phosphate, and as a sample for physiological research on living bones, teeth, and mineralization. It can also be used as an anti-caking agent and flow regulator for other powders, a chromatographic adsorbent for proteins or nucleic acids, a filler for plastics, an ion exchanger, and the like. As described above, according to the present invention, it is possible to achieve the excellent effect of providing a novel composite compound in which an organic acid ion is incorporated into the structure of octacalcium phosphate, and a method for producing the same. Example 1 1 g of α-tricalcium phosphate powder was put into 50 ml of a 0.25 molar malonic acid aqueous solution adjusted to pH 6.4 with aqueous ammonia, and kept at 40°C for 3 hours.
The solid phase was filtered and washed with water, and dried at 40°C. The reaction rate was 45%. The Ca/P molar ratio of the solid phase is
1.47, the basal spacing of its structure is 20.2 Å, and its chemical composition is Ca 8 (PO 4 ) 4 ( HPO 4 ) 1.58
( CH 2 C 2 O 4 ) was equivalent to 0.42 ·5.3H 2 O. Example 2 In Example 1, PH6.4 was changed to PH6.0, and succinic acid was used instead of malonic acid. The reaction rate is 100
It was %. The Ca/P molar ratio of the solid phase is 1.58,
The basal spacing of its structure is 21.4 Å, and its chemical composition is Ca 8 (PO 4 ) 4 (HPO 4 ) 1.06 (C 2 H 4 C 2 O 4 ) 0.94 .
It was equivalent to 5.9H 2 O. Example 3 In Example 2, glutaric acid was used instead of succinic acid. The reaction rate was 60%. solid phase
The Ca/P molar ratio is 1.45, and the basal spacing of the structure is
22.3 Å, and its chemical composition is Ca 8 (PO 4 ) 4
It was equivalent to (HPO 4 ) 1.65 (C 3 H 6 C 2 O 4 ) 0.35 · 5H 2 O. Example 4 In Example 2, adipic acid was used instead of succinic acid. The reaction rate was 100%. The Ca/P molar ratio of the solid phase is 1.44, the basal spacing of its structure is 23.6 Å, and its chemical composition is Ca 8 (PO 4 ) 4
(HPO 4 ) 1.55 (C 4 H 8 C 2 O 4 ) 045.6.6H 2 O equivalent. Example 5 In Example 2, pimelic acid was used instead of succinic acid. The reaction rate was 80%. The Ca/P molar ratio of the solid phase is 1.41, the basal spacing of its structure is 25.1 Å, and its chemical composition is Ca 8 (PO 4 ) 4
It was equivalent to (HPO 4 ) 1.78 (C 5 H 10 C 2 O 4 ) 0.22 · 5.0H 2 O. Example 6 In Example 2, succinic acid was replaced with speric acid. The reaction rate was 70%. The Ca/P molar ratio of the solid phase is 1.55, the basal spacing of its structure is 26.1 Å, and its chemical composition is Ca 8 (PO 4 ) 4
It was equivalent to (HPO 4 ) 1.08 ( C 6 H 12 C 2 O 4 ) 0.92 ·7.6H 2 O.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は本発明の複合化合物の加熱重量減少曲
線、第2図は燐酸八カルシウム、およびそのコハ
ク酸複合化合物の底面間隔の加熱変化曲線、第3
図は本発明の複合化合物の赤外線吸収スペクトル
をそれぞれ示す。
Figure 1 is a heating weight loss curve of the composite compound of the present invention, Figure 2 is a heating change curve of basal spacing of octacalcium phosphate and its succinic acid composite compound, and Figure 3 is a heating weight loss curve of the composite compound of the present invention.
The figures each show the infrared absorption spectra of the composite compounds of the present invention.

Claims (1)

【特許請求の範囲】 1 一般式 Ca8(PO44(HPO42-Z・(Co2oC2O4Z
mH2O (ただし、式中Zは0より大きく1以下の数、
nは1より大きく6以下の整数、mは4〜8の数
を表わす。)で示される燐酸八カルシウムと有機
酸との複合化合物。 2 α―燐酸三カルシウムを一般式Co2oC2O - (ただし、式中nは1より大きく6以下の整数
を表わす)で示される有機酸イオンの共存下、PH
5〜7の下で加水分解することを特徴とする 一般式 Ca8(PO44(HPO42-Z・Co2oC2O4Z
mH2O (ただし、式中Zは0より大きく1以下の数、
nは1より大きく6以下の整数、mは4〜8の数
を表わす)で示される燐酸八カルシウムと有機酸
との複合化合物の製造法。
[Claims] 1 General formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-Z・(C o H 2o C 2 O 4 ) Z
mH 2 O (where Z is a number greater than 0 and less than or equal to 1,
n represents an integer greater than 1 and less than or equal to 6, and m represents a number from 4 to 8. ) A complex compound of octacalcium phosphate and an organic acid. 2 α - Tricalcium phosphate is PH
General formula: Ca 8 (PO 4 ) 4 (HPO 4 ) 2-Z・C o H 2o C 2 O 4 ) Z
mH 2 O (where Z is a number greater than 0 and less than or equal to 1,
n is an integer greater than 1 and less than or equal to 6, and m is a number from 4 to 8).
JP10889283A 1983-06-17 1983-06-17 Complex compound of octacalcium phosphate and organic acid and its production method Granted JPS601188A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10889283A JPS601188A (en) 1983-06-17 1983-06-17 Complex compound of octacalcium phosphate and organic acid and its production method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10889283A JPS601188A (en) 1983-06-17 1983-06-17 Complex compound of octacalcium phosphate and organic acid and its production method

Publications (2)

Publication Number Publication Date
JPS601188A JPS601188A (en) 1985-01-07
JPS6139314B2 true JPS6139314B2 (en) 1986-09-03

Family

ID=14496251

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10889283A Granted JPS601188A (en) 1983-06-17 1983-06-17 Complex compound of octacalcium phosphate and organic acid and its production method

Country Status (1)

Country Link
JP (1) JPS601188A (en)

Also Published As

Publication number Publication date
JPS601188A (en) 1985-01-07

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