JPH04120459A - Analyzing method of hippuric acid - Google Patents
Analyzing method of hippuric acidInfo
- Publication number
- JPH04120459A JPH04120459A JP2240003A JP24000390A JPH04120459A JP H04120459 A JPH04120459 A JP H04120459A JP 2240003 A JP2240003 A JP 2240003A JP 24000390 A JP24000390 A JP 24000390A JP H04120459 A JPH04120459 A JP H04120459A
- Authority
- JP
- Japan
- Prior art keywords
- hippuric acid
- particles
- filler
- carbon
- column
- 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.)
- Pending
Links
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims description 16
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000004811 liquid chromatography Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000012488 sample solution Substances 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003158 alcohol group Chemical group 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- 239000011295 pitch Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polyethylene dimethacrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000011318 synthetic pitch Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、充填剤として炭素系粒子を含む液体クロマト
グラフィーカラムを用いる馬尿酸の分析方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for analyzing hippuric acid using a liquid chromatography column containing carbon-based particles as a filler.
［従来の技術］
馬尿酸は、草食動物の尿中に多量に含まれる物質であり
、ヒト尿中にも含まれる。肝臓における安息香酸の解毒
作用の結果物として尿中に排泄されるので、馬尿酸の分
析により肝臓機能を検査することができる。また、馬尿
酸の分析は、医薬等の中間体の製造のためにも有用であ
る。[Prior Art] Hippuric acid is a substance contained in large amounts in the urine of herbivorous animals, and is also contained in human urine. Since it is excreted in the urine as a result of the detoxification effect of benzoic acid in the liver, liver function can be tested by analyzing hippuric acid. Analysis of hippuric acid is also useful for the production of intermediates for pharmaceuticals and the like.
従来、馬尿酸の検出法としては、イオン交換クロマトグ
ラフィー及び逆相クロマトグラフィーが行なわれている
。イオン交換クロマトグラフィーに用いられる充填剤と
してはシリカ系のものと有機ボリマニ系のものがある。Conventionally, ion exchange chromatography and reverse phase chromatography have been used to detect hippuric acid. There are two types of packing materials used in ion-exchange chromatography: silica-based fillers and organic Borimani-based fillers.
これらのうち、シリカ系の充填剤は、使用可能ｐ■が２
〜８と比較的狭く、これよりも酸性又はアルカリ側で使
用するとシリカの溶出が起き、従って、カラム性能が低
下した際にもアルカリ洗浄による再生を行なうことがで
きない、また、有機ポリマー系の充填剤は、耐圧性、耐
熱性が悪く、また、溶媒により膨潤する性質を有してい
る。また、逆相クロマトグラフィーの充填剤としては、
化学修飾されたシリカ、すなわちいわゆるＯＤＳシリカ
が用いられているが、これについても、上記したシリカ
系充填剤と同様な問題がある。Among these, silica-based fillers have a usable p■ of 2
~8, which is relatively narrow, and if used at a more acidic or alkaline side than this, silica will elute, and therefore, even if the column performance deteriorates, it cannot be regenerated by alkaline cleaning. The agent has poor pressure resistance and heat resistance, and also has the property of being swollen by solvents. In addition, as a packing material for reversed phase chromatography,
Chemically modified silica, ie, so-called ODS silica, is used, but this also has the same problems as the silica-based fillers described above.
［発明が解決しようとする問題点］
従って、本発明の目的は、使用可能なｐＨｔｌが広く、
従って、酸又はアルカリによる再生が可能であり、かつ
、耐圧性、耐熱性及び耐溶媒性に優れた充填剤を用い、
馬尿酸を高感度に分析することができる馬尿酸の分析方
法を提供することである。[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a wide range of usable pHtl,
Therefore, using a filler that can be regenerated by acid or alkali and has excellent pressure resistance, heat resistance, and solvent resistance,
An object of the present invention is to provide a method for analyzing hippuric acid that can analyze hippuric acid with high sensitivity.
［問題点を解決するための手段］
本発明者らは、鋭意研究の結果、炭素系粒子を充填剤と
して含む液体クロマトグラフィーカラムを用いるとき、
分離能が高（馬尿酸を高感度に分析でき、かつ、該充填
剤は使用可能なｐＨ域が広（、従って、酸又はアルカリ
による再生が可能であり、かつ、耐圧性、耐熱性及び耐
溶媒性に優れていることを見出し本発明を完成した。[Means for Solving the Problems] As a result of intensive research, the present inventors found that when using a liquid chromatography column containing carbon-based particles as a filler,
It has high separation ability (hippuric acid can be analyzed with high sensitivity, and the packing material has a wide usable pH range (therefore, it can be regenerated with acid or alkali, and has high pressure resistance, heat resistance, and They found that it has excellent solvent properties and completed the present invention.
すなわち、本発明は、炭素系粒子を充填剤として含む液
体クロマトグラフィーカラムを用いることを特徴とする
馬尿酸の分析方法を提供する。That is, the present invention provides a method for analyzing hippuric acid, which is characterized by using a liquid chromatography column containing carbon-based particles as a filler.
［発明の効果コ
本発明により充填剤として炭素系粒子を含む液体クロマ
トグラフィーによる馬尿酸の分析法が提供された。本発
明の分析法によると、馬尿酸を高感度に分析することが
できる。また、本発明の方法に用いる炭素系粒子は、使
用可能なｐＨ＠が１〜１４と広（、従って、酸又はアル
カリによる再生が可能であり、かつ、耐圧性、耐熱性及
び耐溶媒性に優れている。[Effects of the Invention] The present invention provides a method for analyzing hippuric acid by liquid chromatography containing carbon-based particles as a filler. According to the analysis method of the present invention, hippuric acid can be analyzed with high sensitivity. Furthermore, the carbon-based particles used in the method of the present invention have a usable pH range of 1 to 14 (therefore, they can be regenerated with acids or alkalis, and have good pressure resistance, heat resistance, and solvent resistance. Are better.
［発明の詳細な説明］
本発明の分析法は、充填剤として炭素系粒子を用いるこ
とを特徴とする。[Detailed Description of the Invention] The analytical method of the present invention is characterized by using carbon-based particles as a filler.
本発明に用いる炭素系粒子の細孔容積指数（１０−５０
１／ｆ１−５０１は好ましくは５０％以上、より好まし
くは６０％以上、最も好ましくは８０％以上である。こ
こで、細孔容積指数ｆｌＯ−５０１／ （１−５０１と
は、半径が１０ｎ園ないし５０ｎｍの細孔の容積の和と
半径がｌｎｍないし５０ｎｍの細孔の容積の和との比を
意味する。細孔容積指数＋１０−５０１／（１−５０１
が５０％未満であると液体クロマトグラフィーカラムの
充填剤として用いた場合のクロマトグラフィーの分離能
が低下する。Pore volume index (10-50
1/f1-501 is preferably 50% or more, more preferably 60% or more, most preferably 80% or more. Here, the pore volume index flO-501/ (1-501 means the ratio of the sum of the volumes of pores with a radius of 10 nm to 50 nm and the sum of the volumes of pores with a radius of 1 nm to 50 nm. .Pore volume index +10-501/(1-501
If it is less than 50%, the chromatographic separation ability will decrease when used as a packing material for a liquid chromatography column.
本発明に用いる炭素系粒子の総組孔容積は好ましくは０
．１５−１／ｇ以上、より好ましくは０．２■ｌ／ｇ以
上である。炭素系粒子の総組孔容積が０．１５ｍ１／ｇ
よりも少ないと、溶質を適度に保持することが困難にな
りクロマトグラフィー充填剤として用いた場合の分離能
が低下する。The total combined pore volume of the carbon-based particles used in the present invention is preferably 0.
．． It is at least 15-1/g, more preferably at least 0.2 l/g. Total pore volume of carbon-based particles is 0.15 m1/g
When the amount is less than 1, it becomes difficult to retain the solute appropriately, and the separation ability decreases when used as a chromatography packing material.
本発明に用いる炭素系粒子の半径５０ｎ■以上の細孔の
容積は好ましくは０．１ ｍ１７ｇ以下、より好ましく
は０．０５■１／ｇ以下である。半径５０ｎ−以上の細
孔の容積が０．１ ｍｌ／ｇを越えると粒子の強度が弱
くなり、高圧下で行なう高速液体クロマトグラフィーの
充填剤として用いると粒子が破壊されて再現性良（クロ
マトグラフィー分離を行なうことができなくなるおそれ
がある。The volume of pores with a radius of 50 nm or more in the carbon-based particles used in the present invention is preferably 0.1 m17 g or less, more preferably 0.05 m1/g or less. When the volume of pores with a radius of 50 nm or more exceeds 0.1 ml/g, the strength of the particles becomes weak, and when used as a packing material for high-performance liquid chromatography performed under high pressure, the particles are destroyed, resulting in poor reproducibility (chromatography). There is a risk that graphic separation will not be possible.
なお、以上述べた炭素系粒子中の細孔容積は以下のよう
にして測定されるものである。Note that the pore volume in the carbon-based particles described above is measured as follows.
測定は窒素ガス吸着法による。装置はＯＭＩＣＲＯＮ
ＴＥＣＨＮＯＬＯＧＹ社製ＯＭＮ Ｉ ５ＯＲＰ
３６０ ａｎｄ １００型を用い、計算はＢＪＨ法
（Ｂａｒｒｅｔ −Ｊｏｙｎｅｒ−Ｈａｌｅｎｄａ等に
より提出された方法）によった。Measurement is by nitrogen gas adsorption method. The device is OMICRON
OMN I 5ORP manufactured by TECHNOLOGY
360 and 100 models were used, and the calculation was based on the BJH method (the method proposed by Barrett-Joyner-Halenda et al.).
本発明の分析法に用いる炭素系粒子は、その炭素原子の
含有量が好ましくは９７重量％以上、より好ましくは９
９％以上である。炭素含有率が９７％未満であると炭素
以外の不純物であるＳ、０、Ｈ，Ｎ、メタル等が非特異
吸着点となり、分離能を低下させる。The carbon-based particles used in the analysis method of the present invention preferably have a carbon atom content of 97% by weight or more, more preferably 9% by weight or more.
It is 9% or more. If the carbon content is less than 97%, impurities other than carbon, such as S, O, H, N, metal, etc., become non-specific adsorption points, reducing the separation ability.
また、本発明に用いる炭素系粒子の粒径は、特に限定さ
れないが、通常１μｍないし３０μ諺程度がクロマトグ
ラフィーカラムの充填剤として好ましい。Further, the particle size of the carbon-based particles used in the present invention is not particularly limited, but is usually about 1 μm to 30 μm, preferably as a packing material for a chromatography column.
本発明に用いる炭素系粒子は、以下のようにして製造す
ることができる。The carbon-based particles used in the present invention can be manufactured as follows.
先ず、平均分子量３００以上のピッチと、有機ポリマー
のモノマーと重合開始剤を含む混合物を懸濁重合反応さ
せ、生成したビーズを回収する。First, a mixture containing pitch having an average molecular weight of 300 or more, an organic polymer monomer, and a polymerization initiator is subjected to a suspension polymerization reaction, and the resulting beads are collected.
ここで採用される有機ポリマーとしては実質的に球状の
網状ゲルを形成することができるものであればいずれの
有機ポリマーをも採用することができるが、好ましい有
機ポリマーの例としてポリジビニルベンゼン、ポリトリ
ビニルベンゼン等の芳香族ビニルポリマーやポリエチレ
ンジメタクリレートを挙げることができる。As the organic polymer employed here, any organic polymer can be employed as long as it can form a substantially spherical network gel, but examples of preferred organic polymers include polydivinylbenzene, polyvinylbenzene, and Examples include aromatic vinyl polymers such as trivinylbenzene and polyethylene dimethacrylate.
また、用いられる原料ピッチの平均分子量は好ましくは
３００以上、より好ましくは４００以上である。平均分
子量が３００未満であると、上記した細孔分布特性を有
する粒子を形成することが困難になる。平均分子量はク
ロロホルムを溶媒として一般的な手法である蒸気圧平衡
法を用いて測定する。また、原料としては石油処理工程
中で得られるピッチ、石炭の乾留工程で得られるピッチ
、ナフタリン、ポリ塩化ビニル等から得られる合成ピッ
チを使用できる。Further, the average molecular weight of the raw material pitch used is preferably 300 or more, more preferably 400 or more. When the average molecular weight is less than 300, it becomes difficult to form particles having the above-described pore distribution characteristics. The average molecular weight is measured using the vapor pressure equilibrium method, which is a common method, using chloroform as a solvent. Further, as the raw material, pitch obtained in a petroleum processing process, pitch obtained in a coal carbonization process, synthetic pitch obtained from naphthalene, polyvinyl chloride, etc. can be used.
懸濁重合の条件は基本的に従来の合成樹脂製造の場合と
同様である。出発時における溶媒中の有機モノマーの濃
度は通常２ないし２０重量％、好ましくは４ないし１０
重量％であり、原料ピッチの濃度は通常２ないし２０重
量％であり、好ましくは４ないし１０重量％である。重
合開始剤としては従来と同様、例えばα、α−アゾビス
イソブチロニトリル、過酸化ベンゾイル及び２．２°−
アゾビス−１２，４−ジメチルバレロニトリル）等を用
いることができる。好ましい溶媒は水である。また、従
来と同様、必要に応じてトルエン、キシレン、ベンゼン
及びベンゾニトリルのような有機溶媒を希釈剤として用
いることができる。さらに、必要に応じ、例えばポリビ
ニルアルコール、メチルセルロースのような懸濁安定剤
を加えることもできる。The conditions for suspension polymerization are basically the same as those for conventional synthetic resin production. The starting concentration of organic monomer in the solvent is usually 2 to 20% by weight, preferably 4 to 10% by weight.
The concentration of raw pitch is usually 2 to 20% by weight, preferably 4 to 10% by weight. As the polymerization initiator, as usual, for example, α, α-azobisisobutyronitrile, benzoyl peroxide, and 2.2°-
azobis-12,4-dimethylvaleronitrile) and the like can be used. The preferred solvent is water. Further, as in the past, an organic solvent such as toluene, xylene, benzene, and benzonitrile can be used as a diluent if necessary. Furthermore, if necessary, a suspension stabilizer such as polyvinyl alcohol or methyl cellulose can be added.
有機モノマー ピッチ及び重合開始剤並びに必要に応じ
て希釈剤及び懸濁剤を溶媒中で撹拌して均一な懸濁物な
生ぜしめた後（２０℃以下で高速撹拌することが好まし
い）、通常５０℃ないし９０℃で４時間ないし１０時間
、好ましくは６０℃ないし８０℃で５時間ないし８時間
重合させるる。After stirring the organic monomer pitch, the polymerization initiator, and optionally a diluent and suspending agent in a solvent to form a homogeneous suspension (preferably high-speed stirring at 20°C or lower), Polymerization is carried out at a temperature of 4 to 10 hours at 60 to 90 degrees Celsius, preferably 5 to 8 hours at 60 to 80 degrees Celsius.
上記操作により、有機子ツマ−が重合し、かつ架橋して
実質的に球状の有機ポリマーの網状ゲルが形成され、こ
の網状ゲルの中にピッチが包み込まれた粒子が得られる
のでこれを回収する。回収は、ろ過により行なうことが
できる。By the above operation, the organic polymer is polymerized and crosslinked to form a substantially spherical organic polymer network gel, and particles in which pitch is wrapped in this network gel are obtained, which are collected. . Recovery can be performed by filtration.
次いで、このようにして得られたビーズを不敵化する。The beads thus obtained are then rendered invincible.
不融化はビーズを空気中で２５０’Ｃないし３８０℃程
度に数時間加熱することにより行なうことができる。Infusibility can be achieved by heating the beads in air at about 250'C to 380C for several hours.
次いで、このようにして不融化したビーズを、１１００
℃以上の温度下で、通常、１１００℃ないし３０００℃
の温度下で、真空中又は、アルゴンや窒素等のような不
活性雰囲気下で焼成する。焼成温度が１１００℃未満で
あると、粒子の炭素含量が本発明で規定する９７重量％
に到達しないおそれがある。Next, the beads made infusible in this way were heated to 1100
At temperatures above ℃, usually 1100℃ to 3000℃
, in vacuum or under an inert atmosphere such as argon or nitrogen. When the firing temperature is less than 1100°C, the carbon content of the particles is 97% by weight as defined in the present invention.
may not be reached.
上記のようにして得られた炭素系粒子は、従来のものと
同様の態様で液体クロマトグラフィーカラム、特に高速
液体クロマトグラフィーカラムの充填剤として用いて馬
尿酸を分析することができる。The carbon-based particles obtained as described above can be used as a packing material for a liquid chromatography column, particularly a high-performance liquid chromatography column, in the same manner as conventional ones to analyze hippuric acid.
炭素系粒子はカラムに充填した後液体クロマトグラフィ
ー装置に接続し、高速液体クロマトグラフィーを行なう
。馬尿酸を含む試料液をカラムにかけ、水に可溶で極性
を有する適当な展開溶媒、例えばアセトニトリル、メタ
ノールのようなアルコール類、テトラヒドロフランのよ
うなエーテル類、ジメチルスルホキシド等で展開するこ
とにより、馬尿酸を分離することができる。After the carbon-based particles are packed into a column, they are connected to a liquid chromatography device and subjected to high performance liquid chromatography. By applying a sample solution containing hippuric acid to the column and developing it with a suitable polar developing solvent that is soluble in water, such as acetonitrile, alcohols such as methanol, ethers such as tetrahydrofuran, dimethyl sulfoxide, etc. Uric acid can be separated.
［実施例］ 以下、本発明を実施例に基づきより具体的に説明する。[Example] Hereinafter, the present invention will be explained in more detail based on Examples.
もっとも、本発明は下記実施例に限定されるものではな
い。However, the present invention is not limited to the following examples.
夫亀■ユ
平均分子量６００の減圧蒸留残渣油５体積％、ジビニル
ベン上２５体積％、ポリビニルアルコール１重量％、ア
ゾビスイソブチロニトリル０．２５重量％、トルエン５
体積％及びイオン交換水（残部）からなる混合物を２０
℃以下の温度下でラボラトリ−デイパーザ−を用いて高
速撹拌した０次いで該混合物を撹拌しながら８０℃に６
時間加熱した。次いで生成したビーズをろ過により回収
し、１００℃で乾燥させた。次いでビーズを３５０℃で
３時間空気中で加熱して不融化した。5% by volume of vacuum distillation residue oil with an average molecular weight of 600, 25% by volume of divinylben, 1% by weight of polyvinyl alcohol, 0.25% by weight of azobisisobutyronitrile, 5% by weight of toluene.
A mixture consisting of volume% and ion-exchanged water (remainder)
The mixture was then heated to 80°C with stirring at high speed using a laboratory depurator at a temperature below 6°C.
heated for an hour. The generated beads were then collected by filtration and dried at 100°C. The beads were then heated at 350° C. for 3 hours in air to infusible.
これを窒素ガス雰囲気下、２５００℃で焼成した。焼成
後、ベンゼン中で超音波処理し、メタノール／エーテル
で洗浄し、１００℃で乾燥し、分級し、炭素系粒子を得
た。This was fired at 2500° C. in a nitrogen gas atmosphere. After firing, it was subjected to ultrasonication in benzene, washed with methanol/ether, dried at 100°C, and classified to obtain carbon-based particles.
得られた粒子の元素分析結果は、炭素１００％であり、
水素、酸素、窒素及びイオウは検出されなかった。また
、絵絹孔容積は０．４４４２ ｍｌ／ｇであり、細孔半
径が１〜１００ＩＩの細孔の容積が０．０７６８ ｍｌ
／ｇ 、 １０〜５０ ｎ＋ｍの細孔の容積が０．３
５６９ ｍｌ／ｇ 、 ５０ ｎｍ以上の細孔の容積が
０．０１０５園ｌ／ｇであり、従って、細孔容積指数（
１０−５０１／（ｌ−５０１は８２．３％であった。The elemental analysis result of the obtained particles was 100% carbon,
Hydrogen, oxygen, nitrogen and sulfur were not detected. In addition, the volume of the pores is 0.4442 ml/g, and the volume of pores with a pore radius of 1 to 100 II is 0.0768 ml.
/g, 10-50 n+m pore volume is 0.3
569 ml/g, the volume of pores larger than 50 nm is 0.0105 l/g, and therefore the pore volume index (
10-501/(l-501 was 82.3%.
得られた炭素系粒子を内径４．６ｍｍ 、長さ１００讃
Ｉのステンレススチール製カラムに平衡スラリー法で充
填し、充填カラムを作製した。The obtained carbon-based particles were packed into a stainless steel column with an inner diameter of 4.6 mm and a length of 100 cm by an equilibrium slurry method to prepare a packed column.
本カラムを高速液体クロマトグラフに接続し、移動相と
してアセトニトリル−水（３０ニア ０ （Ｖ／Ｖ）
、 ０．１％ＴＦＡ含有）を高圧下（１１４ｋｇ／ｃｍ
２１流速１ ＋ｎｌ／ ｌ１ｌｉｎで流し、マンデル酸
、馬尿酸及び０−メチル馬尿酸の標準混合物を注入し、
ＵＶ２２０ｎｍで検出しクロマトグラムを得た。This column was connected to a high performance liquid chromatograph, and acetonitrile-water (30 Nia 0 (V/V)) was used as the mobile phase.
, containing 0.1% TFA) under high pressure (114 kg/cm
21 flow rate 1 +nl/llin, injecting a standard mixture of mandelic acid, hippuric acid and 0-methylhippuric acid,
A chromatogram was obtained by detecting with UV 220 nm.
図１から明らかなように本発明の分析法を用いると３つ
の試料成分が明確に分離されている。As is clear from FIG. 1, the three sample components are clearly separated using the analytical method of the present invention.
また、保持時間も短（、馬尿酸類の検出が迅速に行なえ
ることが分かる。In addition, the retention time is short (it is clear that hippuric acids can be detected quickly).
図１は１本発明の分析法による馬尿酸類の高速液体クロ
マトグラフィーの結果を示すクロマトグラムである。FIG. 1 is a chromatogram showing the results of high performance liquid chromatography of hippuric acids according to the analytical method of the present invention.
Claims (3)
フィーカラムを用いることを特徴とする馬尿酸の分析方
法。(1) A method for analyzing hippuric acid, which is characterized by using a liquid chromatography column containing carbon-based particles as a filler.
−５０）が５０％以上、総細孔容積が０．１５ｍｌ／ｇ
以上、半径５０ｎｍ以上の細孔の容積が０．１ｍｌ／ｇ
以下であり、炭素の含量が９７重量％以上であることを
特徴とする請求項１記載の馬尿酸の分析方法。(2) Pore volume index of carbon-based particles (10-50)/(1
-50) is 50% or more, total pore volume is 0.15ml/g
The volume of pores with a radius of 50 nm or more is 0.1 ml/g.
2. The method for analyzing hippuric acid according to claim 1, wherein the carbon content is 97% by weight or more.
０％以上であることを特徴とする請求項２記載の馬尿酸
の分析方法。(3) Pore volume index (10-50)/(1-50) is 8
The method for analyzing hippuric acid according to claim 2, wherein the hippuric acid content is 0% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240003A JPH04120459A (en) | 1990-09-12 | 1990-09-12 | Analyzing method of hippuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240003A JPH04120459A (en) | 1990-09-12 | 1990-09-12 | Analyzing method of hippuric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04120459A true JPH04120459A (en) | 1992-04-21 |
Family
ID=17053020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2240003A Pending JPH04120459A (en) | 1990-09-12 | 1990-09-12 | Analyzing method of hippuric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04120459A (en) |
-
1990
- 1990-09-12 JP JP2240003A patent/JPH04120459A/en active Pending
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