JPH11302288A - New cerium complex - Google Patents
New cerium complexInfo
- Publication number
- JPH11302288A JPH11302288A JP11346498A JP11346498A JPH11302288A JP H11302288 A JPH11302288 A JP H11302288A JP 11346498 A JP11346498 A JP 11346498A JP 11346498 A JP11346498 A JP 11346498A JP H11302288 A JPH11302288 A JP H11302288A
- Authority
- JP
- Japan
- Prior art keywords
- cerium
- complex
- hna
- hydroxynicotinic acid
- nucleic acids
- 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.)
- Withdrawn
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、中性領域の水系で
のペプチドや核酸の加水分解用不均一触媒等として種々
の用途に供することができ得るセリウム（ＩＶ）錯体に
関するものである。The present invention relates to a cerium (IV) complex which can be used for various purposes as a heterogeneous catalyst for hydrolysis of peptides and nucleic acids in a neutral aqueous system.
【０００２】[0002]
【従来の技術】従来、ランタン、セリウムをはじめとす
る希土類金属は、酸化触媒、自動車用排気ガス浄化用触
媒、発光材料、磁性材料等に用いられてきた。しかし、
希土類金属の中で特に４価のセリウムは、ペプチドや核
酸の加水分解反応にて極めて高い反応活性および立体選
択性を持つこと、あるいは一般的にも極めて高い酸化還
元電位を持つこと等が知られているにも関わらず、中性
水中では不安定で水酸化セリウムを生成してゲル化しや
すく、その工業的な利用は、酸化セリウム（ＣｅＯ2 ）
を除いて、強酸性溶液中で水溶液状態での利用に限られ
てきた。2. Description of the Related Art Heretofore, rare earth metals such as lanthanum and cerium have been used as oxidation catalysts, catalysts for purifying automobile exhaust gas, luminescent materials, magnetic materials and the like. But,
Among the rare earth metals, particularly tetravalent cerium is known to have extremely high reaction activity and stereoselectivity in the hydrolysis reaction of peptides and nucleic acids, or generally to have a very high oxidation-reduction potential. Despite this, it is unstable in neutral water and easily forms cerium hydroxide to easily gel, and its industrial use is cerium oxide (CeO 2 )
With the exception of, use in aqueous solutions in strongly acidic solutions has been limited.
【０００３】例えば従来、４価のセリウムは、ペプチド
の加水分解反応用の触媒として用いられてきた。しか
し、最も反応活性が期待できる中性領域ではセリウム自
身が加水分解を引き起こし、水酸化セリウムを主体とし
たゲルを生成し、セリウムと反応生成物との分離、回収
が困難であり、産業的、経済的に問題があった。For example, tetravalent cerium has conventionally been used as a catalyst for a peptide hydrolysis reaction. However, in the neutral region where the most reactive activity can be expected, cerium itself causes hydrolysis, forming a gel mainly composed of cerium hydroxide, and it is difficult to separate and recover cerium and the reaction product. There were financial problems.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
問題を解決し、ｐＨ５〜ｐＨ８の中性水中でゲル化する
ことなくペプチドや核酸の加水分解用不均一触媒となり
得、反応後、反応物と触媒とを分離、回収可能な化合物
として有用で新規なセリウム（ＩＶ）錯体を提供するも
のである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a heterogeneous catalyst for hydrolysis of peptides and nucleic acids without gelation in neutral water at pH 5 to pH 8, and after the reaction, An object of the present invention is to provide a novel cerium (IV) complex which is useful as a compound capable of separating and recovering a reactant and a catalyst.
【０００５】[0005]
【課題を解決するための手段】本発明は、（１）式で示
されるセリウム（ＩＶ）錯体である。The present invention is a cerium (IV) complex represented by the formula (1).
【０００６】[0006]
【化２】［Ｃｅ（ＨＮＡ）4 ］ … （１）式 （ただし、ＨＮＡは２−ヒドロキシニコチン酸イオンを
示す）Embedded image [Ce (HNA) 4 ] (1) where HNA represents 2-hydroxynicotinic acid ion
【０００７】[0007]
【発明の実施の形態】本発明の錯体［Ｃｅ（ＨＮ
Ａ）4 ］は、例えば２−ヒドロキシニコチン酸のナトリ
ウム塩の水溶液に、硝酸セリウム（ＩＶ）アンモニウム
水溶液を加え、析出物を濾過し、水洗し、乾燥すること
により得られる。BEST MODE FOR CARRYING OUT THE INVENTION The complex of the present invention [Ce (HN
A) 4 ] can be obtained, for example, by adding an aqueous solution of cerium (IV) ammonium nitrate to an aqueous solution of sodium salt of 2-hydroxynicotinic acid, filtering the precipitate, washing with water, and drying.
【０００８】あるいは、２−ヒドロキシニコチン酸を８
０℃程度の湯に溶かし、これに硝酸セリウム（ＩＶ）ア
ンモニウム水溶液を加え、室温まで冷却した後、析出物
を濾過し、湯洗、水洗し、乾燥することによっても得ら
れる。Alternatively, 2-hydroxynicotinic acid is
It is also obtained by dissolving in hot water of about 0 ° C., adding an aqueous solution of cerium (IV) ammonium nitrate thereto, cooling the mixture to room temperature, filtering the precipitate, washing with hot water, washing with water and drying.
【０００９】得られた錯体［Ｃｅ（ＨＮＡ）4 ］は、赤
褐色の粉末ないしは木の葉状の結晶であり、固体であ
る。The obtained complex [Ce (HNA) 4 ] is a red-brown powder or a leaf-like crystal and is a solid.
【００１０】用途によっては、２−ヒドロキシニコチン
酸のナトリウム塩の水溶液と硝酸セリウム（ＩＶ）アン
モニウム水溶液の混合速度を変化させることにより、析
出する［Ｃｅ（ＨＮＡ）4 ］の粒子径を０．１μｍ〜数
ｍｍの範囲でコントロールすることができる。In some applications, the particle diameter of precipitated [Ce (HNA) 4 ] is 0.1 μm by changing the mixing speed of the aqueous solution of sodium salt of 2-hydroxynicotinic acid and the aqueous solution of cerium (IV) ammonium nitrate. It can be controlled in the range of up to several mm.
【００１１】本発明の錯体［Ｃｅ（ＨＮＡ）4 ］は、中
性領域の水系でのペプチドや核酸の加水分解用不均一触
媒として使用した後に、濾過あるいは遠心分離等、通常
用いられる方法で反応物と触媒とを容易に分離、回収が
できる。The complex [Ce (HNA) 4 ] of the present invention is used as a heterogeneous catalyst for hydrolysis of peptides and nucleic acids in a neutral aqueous region, and then reacted by a commonly used method such as filtration or centrifugation. The product and the catalyst can be easily separated and recovered.
【００１２】本発明の錯体［Ｃｅ（ＨＮＡ）4 ］は、中
性領域の水系でのペプチドや核酸の加水分解用不均一触
媒以外にも、耐水溶性、耐溶剤性に優れた発色顔料ある
いは金属材料の防食顔料としても用いることができる。The complex [Ce (HNA) 4 ] of the present invention can be used in addition to a heterogeneous catalyst for hydrolyzing peptides and nucleic acids in a neutral aqueous system, as well as a coloring pigment or metal having excellent water resistance and solvent resistance. It can also be used as an anticorrosive pigment for the material.
【００１３】[0013]
【実施例】以下、この発明の実施例について説明する。Embodiments of the present invention will be described below.
【００１４】実施例１ ［Ｃｅ（ＨＮＡ）4 ］結晶の合成 ２−ヒドロキシニコチン酸（分子量１３９．１１、東京
化成工業（株）社製）３４．７７７５ｇを蒸留水１．７
５リットル中に加え、ビーカー中で撹拌しながら約８０
℃に加熱し、完全に溶解する。溶解後、加熱をやめビー
カーを静置し、温度が下がらないうちにあらかじめ調製
した１ｍｏｌ／ｌの硝酸セリウム（ＩＶ）アンモニウム
（Ｃｅ（ＮＨ4 ）2 （ＮＯ3 ）6 、分子量５４８．２
２、関東化学（株）社製）水溶液５０ｃｃをゆっくりと
ビーカーの壁面に沿わせて加え、３日間静置する。３日
後析出した結晶を濾過し、８０℃の蒸留水１０リットル
で未反応の２−ヒドロキシニコチン酸を洗い流した後、
室温に冷却する。冷却後、エタノールで洗浄し、真空乾
燥し、錯体結晶を得た。 Example 1 Synthesis of [Ce (HNA) 4 ] crystal 34.7775 g of 2-hydroxynicotinic acid (molecular weight: 139.11, manufactured by Tokyo Chemical Industry Co., Ltd.) was obtained by distilling 1.7 ml of distilled water.
Add about 5 liters and stir in a beaker for about 80
Heat to ° C. and dissolve completely. After dissolution, the heating was stopped and the beaker was allowed to stand, and 1 mol / l ammonium cerium (IV) nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 , molecular weight 548.2, which had been prepared before the temperature was lowered, was not dissolved.
2. Aqueous solution (manufactured by Kanto Chemical Co., Ltd.) (50 cc) is slowly added along the wall of the beaker, and left to stand for 3 days. After 3 days, the precipitated crystals were filtered, and unreacted 2-hydroxynicotinic acid was washed away with 10 liters of distilled water at 80 ° C.
Cool to room temperature. After cooling, it was washed with ethanol and dried under vacuum to obtain a complex crystal.
【００１５】以下に、得られた錯体の構造決定のための
分析結果を示した。The analysis results for determining the structure of the obtained complex are shown below.
【００１６】（１） 元素分析値(1) Elemental analysis value
【００１７】[0017]
【表１】 [Table 1]
【００１８】（２） ＩＲ（ＫＢｒ錠剤） 得られた錯体の赤外線吸収スペクトルを図１に示した。
比較として２−ヒドロキシニコチン酸、２−ヒドロキシ
ニコチン酸ナトリウム塩の赤外線吸収スペクトルも併せ
て示した。(2) IR (KBr tablet) The infrared absorption spectrum of the obtained complex is shown in FIG.
For comparison, the infrared absorption spectra of 2-hydroxynicotinic acid and 2-hydroxynicotinic acid sodium salt are also shown.
【００１９】２−ヒドロキシニコチン酸では１７３９．
８６ｃｍ-1に認められたカルボニル伸縮振動による吸収
が、得られた錯体では１６３０．７６ｃｍ-1にシフトし
ている（２−ヒドロキシニコチン酸ナトリウム塩では１
６６４．３３ｃｍ-1）。In the case of 2-hydroxynicotinic acid, 1739.
Absorption due to carbonyl stretching vibration was observed at 86cm -1 is the resultant in the complex is shifted to 1630.76cm -1 (2- hydroxy nicotinic acid sodium salt 1
664.33 cm -1 ).
【００２０】以上の結果より、得られた錯体は組成式Ｃ
24Ｈ16Ｎ4 Ｏ12Ｃｅ、分子式［Ｃｅ（Ｃ6 Ｈ4 ＮＯ3 ）
4 ］で示すことのできるＣｅ原子１個と２−ヒドロキシ
ニコチン酸イオン４分子からなる錯体であることがわか
った。From the above results, the obtained complex was represented by the composition formula C
24 H 16 N 4 O 12 Ce, molecular formula [Ce (C 6 H 4 NO 3 )
4 ], and was found to be a complex consisting of one Ce atom and four molecules of 2-hydroxynicotinic acid ions.
【００２１】実施例２ （１） ［Ｃｅ（ＨＮＡ）4 ］粉末の合成 ２−ヒドロキシニコチン酸（分子量１３９．１１、東京
化成工業（株）社製）３４．７７７５ｇを蒸留水１．７
５リットル中に加え、撹拌しながらｐＨ＝６．８になる
まで５Ｎ ＮａＯＨ水溶液を滴下し、完全に溶解する。
これにあらかじめ調製した１ｍｏｌ／ｌの硝酸セリウム
（ＩＶ）アンモニウム（Ｃｅ（ＮＨ4 ）2 （Ｎ
Ｏ3 ）6 、分子量５４８．２２、関東化学（株）社製）
水溶液５０ｃｃを一気に加えると、赤褐色の錯体［Ｃｅ
（ＨＮＡ）4 ］が析出する。得られた析出物をメンブレ
ンフィルターで吸引濾過し、８０℃の蒸留水１０リット
ルで洗浄した後、蒸留水１０リットルで洗浄した。水洗
後、エタノールで洗浄し、真空乾燥し、目的の錯体粉末
を得た。平均粒径は０．１２μｍであった。 Example 2 (1) Synthesis of [Ce (HNA) 4 ] Powder 34.7775 g of 2-hydroxynicotinic acid (molecular weight: 139.11; manufactured by Tokyo Chemical Industry Co., Ltd.) was obtained by distilling 1.7 parts of distilled water.
Add to 5 liters and add dropwise 5N NaOH aqueous solution with stirring until pH = 6.8 and dissolve completely.
1 mol / l cerium (IV) ammonium nitrate (Ce (NH 4 ) 2 (N
O 3 ) 6 , molecular weight 548.22, manufactured by Kanto Chemical Co., Ltd.)
When 50 cc of the aqueous solution is added at once, a reddish brown complex [Ce
(HNA) 4 ] precipitates. The obtained precipitate was filtered by suction with a membrane filter, washed with 10 liters of distilled water at 80 ° C., and then washed with 10 liters of distilled water. After washing with water, it was washed with ethanol and dried under vacuum to obtain the desired complex powder. The average particle size was 0.12 μm.
【００２２】（２） ペプチドの加水分解 アラニルグリシルフェニルアラニンの１０ｍｍｏｌ／ｌ
の水溶液にＣｅが１０ｍｍｏｌ／ｌになるように（１）
で合成した［Ｃｅ（ＨＮＡ）4 ］の粉末（分子量６９
２．５３）を加えて分散し、ｐＨ７．２、６０℃で７２
時間反応させた。反応後、反応液を濾過して［Ｃｅ（Ｈ
ＮＡ）4 ］を回収した後、濾液中のアミノ酸を定量し加
水分解反応率を求めたところ、１１％であった。また、
［Ｃｅ（ＨＮＡ）4 ］の回収率は９４％であった。(2) Hydrolysis of peptide 10 mmol / l of alanylglycylphenylalanine
So that Ce becomes 10 mmol / l in the aqueous solution of (1).
[Ce (HNA) 4 ] powder (molecular weight 69)
2.53), and dispersed at pH 7.2 at 60 ° C. for 72 hours.
Allowed to react for hours. After the reaction, the reaction solution was filtered and [Ce (H
After recovering NA) 4 ], the amino acid in the filtrate was quantified and the hydrolysis reaction rate was determined to be 11%. Also,
The recovery rate of [Ce (HNA) 4 ] was 94%.
【００２３】比較として［Ｃｅ（ＨＮＡ）4 ］の代わり
に硝酸セリウム（ＩＶ）アンモニウムを用いて同様に反
応させたところ、ゲルを生成し、セリウムとアミノ酸あ
るいはアラニルグリシルフェニルアラニンの分離ができ
なかった。As a comparison, when the same reaction was carried out using cerium (IV) ammonium nitrate instead of [Ce (HNA) 4 ], a gel was formed, and separation of cerium from amino acids or alanylglycylphenylalanine could not be performed. .
【００２４】[0024]
【発明の効果】本発明のセリウム（ＩＶ）錯体［Ｃｅ
（ＨＮＡ）4 ］は、ｐＨ５〜ｐＨ８の中性水中でゲル化
することなく安定に固体状態として存在するため、中性
領域の水系でのペプチドや核酸の加水分解用不均一触媒
等として種々の用途に供することができる。The cerium (IV) complex of the present invention [Ce
(HNA) 4 ] exists in a solid state stably without gelation in neutral water at pH 5 to pH 8, and therefore various heterogeneous catalysts and the like for hydrolysis of peptides and nucleic acids in an aqueous system in a neutral region are used. Can be used for applications.
【図１】本発明の錯体［Ｃｅ（ＨＮＡ）4 ］の赤外吸収
スペクトル、及び、比較として２−ヒドロキシニコチン
酸、２−ヒドロキシニコチン酸ナトリウム塩の赤外線吸
収スペクトルを示す。FIG. 1 shows an infrared absorption spectrum of the complex [Ce (HNA) 4 ] of the present invention, and an infrared absorption spectrum of 2-hydroxynicotinic acid and sodium 2-hydroxynicotinate as a comparison.
Claims (1)
Ｖ）錯体。 【化１】［Ｃｅ（ＨＮＡ）4 ］ … （１）式 （ただし、ＨＮＡは２−ヒドロキシニコチン酸イオンを
示す）Cerium (I) represented by the following formula (1)
V) Complex. Embedded image [Ce (HNA) 4 ] (1) where HNA represents 2-hydroxynicotinic acid ion
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11346498A JPH11302288A (en) | 1998-04-23 | 1998-04-23 | New cerium complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11346498A JPH11302288A (en) | 1998-04-23 | 1998-04-23 | New cerium complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11302288A true JPH11302288A (en) | 1999-11-02 |
Family
ID=14612915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11346498A Withdrawn JPH11302288A (en) | 1998-04-23 | 1998-04-23 | New cerium complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11302288A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013154261A (en) * | 2012-01-26 | 2013-08-15 | Toyota Motor Corp | Promoter for exhaust gas purification and production process therefor |
| CN106466642A (en) * | 2016-09-30 | 2017-03-01 | 上海理工大学 | A kind of Ce Base Metal organic framework catalyst, its preparation method and the application in Air Pollution prevention and control |
-
1998
- 1998-04-23 JP JP11346498A patent/JPH11302288A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013154261A (en) * | 2012-01-26 | 2013-08-15 | Toyota Motor Corp | Promoter for exhaust gas purification and production process therefor |
| CN106466642A (en) * | 2016-09-30 | 2017-03-01 | 上海理工大学 | A kind of Ce Base Metal organic framework catalyst, its preparation method and the application in Air Pollution prevention and control |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20050705 |