JPH0781997B2 - Spherical packing material for liquid chromatography - Google Patents
Spherical packing material for liquid chromatographyInfo
- Publication number
- JPH0781997B2 JPH0781997B2 JP61158411A JP15841186A JPH0781997B2 JP H0781997 B2 JPH0781997 B2 JP H0781997B2 JP 61158411 A JP61158411 A JP 61158411A JP 15841186 A JP15841186 A JP 15841186A JP H0781997 B2 JPH0781997 B2 JP H0781997B2
- Authority
- JP
- Japan
- Prior art keywords
- filler
- liquid chromatography
- packing material
- calcium phosphate
- present
- 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 - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
Description
【発明の詳細な説明】 「技術分野」 本発明は、例えば単糖類、オリゴ糖類などの分離に好適
な液体クロマトグラフィー用球状充填剤に関する。TECHNICAL FIELD The present invention relates to a spherical packing material for liquid chromatography, which is suitable for separating monosaccharides, oligosaccharides and the like.
「従来技術およびその問題点」 液体クロマトグラフィー用充填剤としては、従来からシ
リカゲル、化学修飾シリカゲル、合成高分子ゲル、天然
高分子ゲル、カーボンゲルなどからなるものが知られて
いる。また、これらの充填剤を多孔質にした多孔質シリ
カ、化学修飾多孔質シリカ、多孔質高分子なども知られ
ている。"Prior art and its problems" As a packing material for liquid chromatography, those made of silica gel, chemically modified silica gel, synthetic polymer gel, natural polymer gel, carbon gel and the like have been conventionally known. Further, porous silica in which these fillers are made porous, chemically modified porous silica, porous polymer and the like are also known.
一方、リン酸カルシウム系化合物、特に合成ハイドロキ
シアパタイト（Ca10（PO4）６（OH）２）は、歯や骨の
無機主成分と同質であり、その優れた生体親和性を応用
して合成ハイドロキシアパタイトにより人工歯根や骨補
填剤が開発されている。この生体と深く関わりをもつリ
ン酸カルシウム系化合物を液体クロマトグラフィーの充
填剤として利用しようとする試みは古くから行われてお
り、蛋白質、酵素などの分離に応用されている。また、
近年においては、製法や形状に特徴を有する充填剤も提
案されている（特開昭60−143762号）。On the other hand, calcium phosphate compounds, especially synthetic hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ) is the same quality as the inorganic main component of teeth and bones, and synthetic hydroxyapatite is applied by applying its excellent biocompatibility. Has developed artificial tooth roots and bone filling materials. Attempts have been made for a long time to utilize the calcium phosphate compound closely related to the living body as a packing material for liquid chromatography, and it has been applied to the separation of proteins and enzymes. Also,
In recent years, a filler characterized by a manufacturing method and a shape has also been proposed (JP-A-60-143762).
ところで、従来のリン酸カルシウム系化合物は、主とし
て蛋白質、酵素などの分離を目的としており、比表面積
を大きくしてその分離性能を高めるため、殆どが多孔質
のものであった。By the way, the conventional calcium phosphate compounds are mainly for the purpose of separating proteins, enzymes, etc., and most of them are porous in order to increase the specific surface area and enhance the separating performance.
本発明者らは、ハイドロキシアパタイトなどのリン酸カ
ルシウム系化合物を充填剤として、蛋白質や酵素以外の
成分を分離しようと試みた結果、リン酸カルシウム系化
合物が糖の分離にも有効であることを見出した。この場
合、分離パターンは、分子量の小さい順に分離されるも
のであることもわかった。The present inventors have attempted to separate components other than proteins and enzymes by using a calcium phosphate-based compound such as hydroxyapatite as a filler, and have found that the calcium phosphate-based compound is also effective for sugar separation. In this case, it was also found that the separation patterns were separated in ascending order of molecular weight.
一方、多孔質の充填剤がゲルパーミエーションクロマト
グラフィーに用いられることは、特開昭50−155290号な
どからも明らかである。ここで、ゲルパーミエーション
クロマトグラフィーとは、分子量の大きい順に分離して
くるものである。On the other hand, it is also clear from JP-A-50-155290 that the porous filler is used for gel permeation chromatography. Here, gel permeation chromatography refers to separation in the order of increasing molecular weight.
そこで、リン酸カルシウム系化合物を充填剤として糖の
分離に適用した場合、充填剤が多孔質のものであると、
上記のゲルパーミエーション的性質が共存することにな
り、その分離性能が低下することがわかった。Therefore, when a calcium phosphate-based compound is applied to the separation of sugar as a filler, the filler is porous,
It was found that the above gel permeation properties coexist and the separation performance thereof deteriorates.
「発明の目的」 本発明の目的は、リン酸カルシウム系化合物を材質とす
る充填剤であって、糖などの分離に適するものを提供す
ることにある。"Object of the Invention" An object of the present invention is to provide a filler made of a calcium phosphate compound, which is suitable for separating sugars and the like.
「発明の構成」 本発明の液体クロマトグラフィー用球状充填剤はCa
10（PO4）６（OH）２、Ca3（PO4）２、Ca2P2O7、Ca（PO
3）２、Ca10（PO4）6F2、Ca10（PO4）6Cl2のうちから選
ばれた一種または二種以上を材質とし、全体としてほぼ
球状をなすと共に、気孔率５％以下の緻密質とされてい
ることを特徴とする。"Structure of the Invention" The spherical filler for liquid chromatography of the present invention is Ca
10 (PO 4 ) 6 (OH) 2 , Ca 3 (PO 4 ) 2 , Ca 2 P 2 O 7 , Ca (PO
3 ) 2 , Ca 10 (PO 4 ) 6 F 2 and Ca 10 (PO 4 ) 6 Cl 2 are made of one or more selected materials, which are almost spherical as a whole and have a porosity of 5%. It is characterized by the following compactness.
このように、本発明では、気孔率５％以下の緻密質の形
状体を用いるようにしたので、ゲルパーミエーション的
性質が少なくなり、分子量の小さい順に分離される糖な
どの分離に適したものとなる。As described above, according to the present invention, since the compact shaped body having the porosity of 5% or less is used, the gel permeation property is reduced, which is suitable for the separation of sugars and the like which are separated in the ascending order of the molecular weight. Becomes
本発明の充填剤は、Ca10（PO4）６（OH）２、Ca3（P
O4）２、Ca2P2O7、Ca（PO3）２、Ca10（PO4）6F2、Ca10
（PO4）6Cl2のうちから選ばれた一種または二種以上を
材質とする。これらのリン酸カルシウム系化合物は、水
溶性のリン酸塩と水溶性のカルシウム塩とを水溶液中で
反応させる湿式合成法や、リン酸化合物とカルシウム化
合物とを高温下で反応させる乾式合成法など、公知の各
種の方法で合成することができる。The filler of the present invention comprises Ca 10 (PO 4 ) 6 (OH) 2 and Ca 3 (P
O 4 ) 2 , Ca 2 P 2 O 7 , Ca (PO 3 ) 2 , Ca 10 (PO 4 ) 6 F 2 , Ca 10
The material is one or more selected from (PO 4 ) 6 Cl 2 . These calcium phosphate-based compounds are known, such as a wet synthesis method of reacting a water-soluble phosphate salt and a water-soluble calcium salt in an aqueous solution, a dry synthesis method of reacting a phosphate compound and a calcium compound at high temperature, and the like. Can be synthesized by various methods.
上記リン酸カルシウム系化合物は、例えば噴霧乾燥造粒
法、回転転動造粒法などの各種手段でほぼ球形に造粒さ
れる。噴霧乾燥造粒法は、リン酸カルシウム系化合物を
水に分散したスラリーを100〜250℃程度で噴霧乾燥し、
ほぼ地形に造粒する方法である。回転転動造粒法は、リ
ン酸カルシウム系化合物粒子をプレート上に載せ、回転
しながら凝集させて造粒する方法である。The calcium phosphate compound is granulated into a substantially spherical shape by various means such as a spray drying granulation method and a rotary tumbling granulation method. The spray-drying granulation method is spray-drying a slurry in which a calcium phosphate compound is dispersed in water at about 100 to 250 ° C.,
It is a method of granulating almost to the terrain. The rotary tumbling granulation method is a method in which calcium phosphate-based compound particles are placed on a plate and agglomerated while rotating to granulate.
こうして造粒した後、900〜1400℃で焼成することによ
り、全体としてほぼ球状をなし、気孔率５％以下の本発
明の充填剤を得ることができる。この場合、焼成温度が
900℃未満では、気孔率が５％を超えやすくなり、ゲル
パーミエーション的性質がでてきて糖などの分離に適さ
なくなる。また、焼成温度が1400℃を超えると、リン酸
カルシウム系化合物が分解反応を起こすので、分離能が
低下する。After granulating in this way, baking at 900 to 1400 ° C. makes it possible to obtain the filler of the present invention having a substantially spherical shape as a whole and having a porosity of 5% or less. In this case, the firing temperature
If the temperature is lower than 900 ° C, the porosity tends to exceed 5% and the gel permeation property appears to make it unsuitable for separating sugars. Further, if the firing temperature exceeds 1400 ° C., the calcium phosphate-based compound causes a decomposition reaction, so that the separability decreases.
なお、本発明の充填剤は、完全な球状である必要はな
く、卵形、ラグビーボール形など球状に近い形状であれ
ばよい。It should be noted that the filler of the present invention does not have to be perfectly spherical, and may have an almost spherical shape such as an egg shape or a rugby ball shape.
また、充填剤の平均粒径は、特に限定されないが、１〜
100μｍ程度とするのが好ましい。平均粒径が１μｍ未
満ではカラムの通液抵抗が大きくなり、100μｍを超え
ると分離能が低下する傾向がある。The average particle size of the filler is not particularly limited,
It is preferably about 100 μm. If the average particle size is less than 1 μm, the liquid passage resistance of the column increases, and if it exceeds 100 μm, the resolution tends to decrease.
本発明の充填剤は、例えばブドウ糖などの単糖類、ショ
糖、乳糖、ラフィノースなどのオリゴ糖類などの分離に
特に有効である。この場合、分子量の小さいものから順
に分離される分離パターンをなす。The filler of the present invention is particularly effective for separating monosaccharides such as glucose, sucrose, lactose, and oligosaccharides such as raffinose. In this case, the separation pattern is such that the ones with the smallest molecular weight are separated in order.
「発明の実施例」 リン酸塩溶液とカルシウム塩溶液とを公知の方法によっ
て反応させ、ハイドロキシアパタイトスラリーを得た。
このスラリーをモービルマイナー型スプレードライヤー
（アシザワニロ製）を用いて噴霧乾燥造粒した。こうし
て得られたほぼ球形の造粒物を1100℃で４時間焼成して
本発明による充填剤を得た。この充填剤は、平均粒径５
μｍ、気孔率１％であった。なお、この充填剤の15000
倍の電子顕微鏡写真を第１図に示す。"Examples of the Invention" A phosphate solution and a calcium salt solution were reacted by a known method to obtain a hydroxyapatite slurry.
This slurry was spray-dried and granulated using a mobile minor type spray dryer (manufactured by Ashizawa Niro). The substantially spherical granules thus obtained were calcined at 1100 ° C. for 4 hours to obtain the filler according to the present invention. This filler has an average particle size of 5
It was μm and the porosity was 1%. In addition, 15,000 of this filler
A double electron micrograph is shown in FIG.
この充填剤を、直径7.5mm、長さ100mmの高速液体クロマ
トグラフィー用ステンレス製カラムに充填し、アセトニ
トリル80％水溶液を溶離液として流速は1.5ml/分で流し
つつ、グルコースとサッカロースの分離を行なったとこ
ろ、第２図に示すようなクロマトグラムが得られた。第
２図において、縦軸は波長195nmにおける吸光度であ
り、横軸は時間（分）である。また、第２図中、Ｇはグ
ルコースを示すピーク、Ｓはサッカロースを示すピーク
である。このように、本発明の充填剤によれば、糖類を
明確に分離できることがわかる。This packing material was packed in a stainless steel column for high performance liquid chromatography with a diameter of 7.5 mm and a length of 100 mm, and 80% aqueous acetonitrile solution was used as an eluent at a flow rate of 1.5 ml / min to separate glucose and saccharose. As a result, a chromatogram as shown in FIG. 2 was obtained. In FIG. 2, the vertical axis is the absorbance at a wavelength of 195 nm, and the horizontal axis is the time (minutes). Further, in FIG. 2, G is a peak showing glucose and S is a peak showing saccharose. Thus, according to the filler of the present invention, it can be seen that sugars can be clearly separated.
「発明の効果」 以上説明したように、本発明の充填剤によれば、リン酸
カルシウム系化合物からなり、全体としてほぼ球状をな
し、気孔率５％以下の緻密質とされているので、ゲルパ
ーミエーション的性質が抑えられ、分子量の小さい方か
ら順に分離される糖などの分離に適したものとなる。[Advantages of the Invention] As described above, according to the filler of the present invention, it is composed of a calcium phosphate-based compound, has a substantially spherical shape as a whole, and is a dense substance having a porosity of 5% or less. It is suitable for the separation of sugars and the like, which are suppressed in their physical properties and are sequentially separated from the one having the smallest molecular weight.
第１図は本発明の実施例による充填剤の粒子構造を示す
15000倍の電子顕微鏡写真、第２図は同充填剤を用いた
液体クロマトグラフィーによりグルコースとサッカロー
スとを分離した結果を示すクロマトグラムである。FIG. 1 shows a particle structure of a filler according to an embodiment of the present invention.
15,000 times electron micrograph, FIG. 2 is a chromatogram showing the result of separating glucose and saccharose by liquid chromatography using the same packing material.
フロントページの続き (72)発明者 澄田 政哉 東京都板橋区前野町２丁目36番９号 旭光 学工業株式会社内 (72)発明者 横尾 明彦 東京都板橋区前野町２丁目36番９号 旭光 学工業株式会社内 (72)発明者 河村 克己 東京都板橋区前野町２丁目36番９号 旭光 学工業株式会社内 (56)参考文献 特開 昭62−206445（ＪＰ，Ａ)Front Page Continuation (72) Inventor Masaya Sumita 2-36 Maenocho, Itabashi-ku, Tokyo Asahi Kogaku Kogyo Co., Ltd. (72) Inventor Akihiko Yokoo 2-36-9 Maenocho, Itabashi-ku, Tokyo Asahi Kogaku Kogyo Co., Ltd. (72) Inventor Katsumi Kawamura 2-36 Maenocho, Itabashi-ku, Tokyo Asahi Kogaku Kogyo Co., Ltd. (56) Reference JP-A-62-206445 (JP, A)
Claims (1)
a2P2O7、Ca（PO3）２、Ca10（PO4）6F2、Ca10（PO4）6C
l2のうちから選ばれた一種または二種以上を材質とし、
全体としてほぼ球状をなすと共に、気孔率５％以下の緻
密質とされていることを特徴とする液体クロマトグラフ
ィー用球状充填剤。1. Ca 10 (PO 4 ) 6 (OH) 2 , Ca 3 (PO 4 ) 2 , C
a 2 P 2 O 7 , Ca (PO 3 ) 2 , Ca 10 (PO 4 ) 6 F 2 , Ca 10 (PO 4 ) 6 C
Made of one or more materials selected from l 2 ,
A spherical packing material for liquid chromatography, which has a substantially spherical shape as a whole and is a dense material having a porosity of 5% or less.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158411A JPH0781997B2 (en) | 1986-07-05 | 1986-07-05 | Spherical packing material for liquid chromatography |
| SE8702760A SE466836B (en) | 1986-07-05 | 1987-07-03 | SPHERICAL FILLING MATERIAL FOR HYDROCHROMATOGRAPHY, PROCEDURE FOR PREPARING THE FILLING MATERIAL AND APPLICATION OF THIS FOR HYDROCHROMATOGRAPHY |
| DE19873722103 DE3722103A1 (en) | 1986-07-05 | 1987-07-03 | Spherical packing for liquid chromatography |
| US07/461,854 US5039408A (en) | 1986-07-05 | 1990-01-08 | Packing material for liquid chromatography |
| US08/029,940 US5441635A (en) | 1986-07-05 | 1993-03-10 | Packing material for liquid chromatography |
| US08/105,850 USRE35340E (en) | 1986-07-05 | 1993-08-13 | Packing material for liquid chromatography |
| US08/371,378 US5651882A (en) | 1986-07-05 | 1995-01-11 | Packing material for liquid chromatography and process for producing the same |
| US08/371,205 US6306297B1 (en) | 1968-07-08 | 1995-01-11 | Packing material for liquid chromatography and process for producing the same |
| US08/469,731 US5651884A (en) | 1986-07-05 | 1995-06-06 | Packing material for liquid chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158411A JPH0781997B2 (en) | 1986-07-05 | 1986-07-05 | Spherical packing material for liquid chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6316046A JPS6316046A (en) | 1988-01-23 |
| JPH0781997B2 true JPH0781997B2 (en) | 1995-09-06 |
Family
ID=15671166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61158411A Expired - Lifetime JPH0781997B2 (en) | 1968-07-08 | 1986-07-05 | Spherical packing material for liquid chromatography |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0781997B2 (en) |
| DE (1) | DE3722103A1 (en) |
| SE (1) | SE466836B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5441635A (en) * | 1986-07-05 | 1995-08-15 | Asahi Kogaku Kogyo Kabushiki Kaisha | Packing material for liquid chromatography |
| JPS6413453A (en) * | 1987-07-08 | 1989-01-18 | Asahi Optical Co Ltd | Packing agent for liquid chromatography |
| US5039408A (en) * | 1986-07-05 | 1991-08-13 | Asahi Kogaku Kogyo K.K. | Packing material for liquid chromatography |
| USRE35340E (en) * | 1986-07-05 | 1996-10-01 | Asahi Kogaku Kogyo K.K. | Packing material for liquid chromatography |
| JPH01162148A (en) * | 1987-12-18 | 1989-06-26 | Asahi Optical Co Ltd | Packing agent for liquid chromatography and its preparation |
| JPH01218579A (en) * | 1988-02-25 | 1989-08-31 | Sekisui Plastics Co Ltd | Decoloring agent for whisky |
| US5728463A (en) * | 1992-08-07 | 1998-03-17 | Kanto Kagaku Kabushiki Kaisha | Stationary phase material for chromatography |
| DE607459T1 (en) * | 1992-08-07 | 1995-04-20 | Kanto Kagaku | MATERIAL FOR CHROMATOGRAPHIC STATIONARY PHASE. |
| JP5463537B2 (en) * | 2008-02-22 | 2014-04-09 | ＨＯＹＡ Ｔｅｃｈｎｏｓｕｒｇｉｃａｌ株式会社 | Separation method |
| CN115135392A (en) * | 2020-02-19 | 2022-09-30 | 生物辐射实验室股份有限公司 | Method for preparing polymer-packed chromatography resins |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762674B2 (en) * | 1986-03-07 | 1995-07-05 | 株式会社高研 | Chromatographic adsorbent, method for producing the same, and chromatographic column using the adsorbent |
-
1986
- 1986-07-05 JP JP61158411A patent/JPH0781997B2/en not_active Expired - Lifetime
-
1987
- 1987-07-03 SE SE8702760A patent/SE466836B/en not_active IP Right Cessation
- 1987-07-03 DE DE19873722103 patent/DE3722103A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3722103C2 (en) | 1991-10-17 |
| DE3722103A1 (en) | 1988-01-14 |
| JPS6316046A (en) | 1988-01-23 |
| SE8702760D0 (en) | 1987-07-03 |
| SE8702760L (en) | 1988-01-06 |
| SE466836B (en) | 1992-04-13 |
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