US20100213411A1 - Monolith separation medium for chromatography and process for producing the same - Google Patents

Monolith separation medium for chromatography and process for producing the same Download PDF

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US20100213411A1
US20100213411A1 US12/160,706 US16070606A US2010213411A1 US 20100213411 A1 US20100213411 A1 US 20100213411A1 US 16070606 A US16070606 A US 16070606A US 2010213411 A1 US2010213411 A1 US 2010213411A1
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separation medium
medium according
monolith
epoxy compound
producing
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Ken Hosoya
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Shimadzu Corp
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Shimadzu Corp
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    • 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
    • B01J20/285—Porous sorbents based on polymers
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/291—Gel 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/82—Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/84—Capillaries
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/50—Conditioning of the sorbent material or stationary liquid
    • G01N30/52—Physical parameters
    • G01N2030/524—Physical parameters structural properties
    • G01N2030/528—Monolithic sorbent material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995—Constituent is in liquid form

Definitions

  • the present invention relates to a monolith separation medium for chromatography having a co-continuous structure comprising a skeletal phase enriched in an organic matter and a pore being continuous in the form of three-dimensional network, and to a process for producing the same.
  • Monoliths mainly comprising silica gel realize high performance due to their fine structural control, and some of them are commercially available.
  • polymer monoliths are produced basically by combining hydrophobic monomer components such as styrene/divinylbenzene with, for example, a porogen which serves as a poor solvent for such monomers as represented by a patent to Svec, et al. (U.S. Pat. No. 5,453,185).
  • the van der Waals force between polymer chains is basically greater than the steric hindrance of growing polymer chains, resulting in flocculation of polymer chains.
  • this causes generation of nuclei due to polymer chain entanglement, growth of microgel particles due to polymer chain flocculation, and rapid increase in surface energy of the system.
  • microgel particles aggregate together, so that the gel continues similar growth (fractal) to get coarser. Therefore, such a system composed of a monomer and a poor solvent is characterized in that gel grows in the form of particle aggregation, and phase separation occurs extremely early in competition with gelation and a monolith form where macroporous pores have a small specific surface area is fixed, resulting in a particle aggregation type monolith. Therefore, conventional monoliths have no skeletal structure and inherently have some problems, such as large maze factors of a through pore, increase in back pressure at high flow rate, and morphological change due to monolith compressibility.
  • the present invention is made for solving the problems with the above-described conventional organic polymer monolith columns, and an object thereof is to provide a non-particle-aggregation-type organic polymer monolith, which serves as a separation medium, and a process for producing the same.
  • a porous material having an extremely uniform skeletal structure can be obtained by dissolving an epoxy compound having a specific molecular structure in a porogen; adding an amine compound of bi- or higher functionality thereto and heating them to polymerize, thereby causing the resulting polymer and the porogen to undergo spinodal decomposition; crosslinking the materials stably before they transit to a particle-aggregation structure due to the growth of phase separation, thereby freezing a non-particle-aggregation-type co-continuous structure; and subsequently removing the porogen. It was also found that the resulting porous material can serve as a separation medium which develops an extremely high theoretical plate number due to the uniformity of the skeleton thereof. As a result, the present invention has been accomplished.
  • the organic macromolecular gel-like monolith separation medium for chromatography of the present invention comprises a skeletal phase, a pore which is formed by the skeletal phase and which is continuous in the form of three-dimensional network, and a functional group present on the surface of the skeletal phase and permitting introduction of a new functional group.
  • the skeletal phase has an average diameter of submicron to micrometer size, and a non-particle-aggregation-type co-continuous structure.
  • the skeletal phase is constituted of an addition polymer from an epoxy compound of bi- or higher functionality and an amine compound of bi- or higher functionality, enriched in an organic matter, and does not contain any carbon atom derived from aromatic series.
  • the functional group present on the surface of the skeletal phase and permitting introduction of a new functional group includes a hydroxyl group produced by a reaction between an epoxy group and an amino group, and an amino group or an epoxy group remaining unreacted.
  • a preferable example of the epoxy compound is 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate.
  • 2,2,2-Tri-(2,3-epoxypropyl)-isocyanurate is a chiral compound which includes optical antipodes.
  • both a racemic mixture and an optically active substance can be used.
  • a chiral compound can be used also as the amine compound. Both a racemic mixture and an optically active substance can be used also as the amine compound.
  • Separation columns for high-performance liquid chromatography comprising the separation medium have 50,000 or more theoretical plates per meter of column length.
  • Separation media for optical resolution aiming at separation of the S-isomer and the R-isomer of optical antipodes by liquid chromatography are resultant monolitic separation media produced by the use of optically active substances as both an epoxy compound and an amine compound.
  • the polymer of the present invention in which optically active substances are used for both an epoxy compound and an amine compound contains an optically active site in its main chain despite being a synthetic macromolecule, and it therefore is an extremely rare separation medium. Moreover, it has a wide range of variations because it is possible to give an optically active site to monomer units of both the epoxy compound and the amine compound.
  • the production process of the present invention is a process for producing the monolith separation medium of the present invention. It has the following steps (A) to (C):
  • the polymerization temperature in the porogen is a temperature suitable for the epoxy compound and the amine compound to dissolve in the porogen and undergo a polymerization reaction. It may be set appropriately depending upon the types of the epoxy compound, the amine compound and the poregon.
  • a preferable example of the epoxy compound used in the production process is 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate.
  • This epoxy compound may be either a racemic mixture or an optically active substance.
  • the amine compound which is a component to be used as a hardener, may be either a racemic mixture or an optically active substance, and examples thereof include an aliphatic amine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine and polyether diamine, an alicyclic polyamine such as isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiron, bis(4-aminocyclohexyl)methane and a modified product thereof, and an aliphatic polyamidoamines composed of a polyamine and a dimmer acid.
  • an aliphatic amine such as
  • alicyclic amine compounds having two or more primary amines in the molecule, and particularly preferred are bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane and the like.
  • a porogen is a solvent which can dissolve an epoxy compound and a hardener and can produce a reaction-inducing phase separation after the polymerization of the epoxy compound and the hardener.
  • the porogen include cellosolves such as methyl cellosolve and ethylcellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and glycols such as polyethylene glycol and polypropylene glycol.
  • cellosolves such as methyl cellosolve and ethylcellosolve
  • esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate
  • glycols such as polyethylene glycol and polypropylene glycol.
  • polyethylene glycol having a molecular weight of 600 or less is preferred, and especially, polyethylene glycol having a molecular weight of 300 or less is preferred.
  • the raw material formulation of the amine to the epoxy compound in molar ratio is suitably within an epoxy compound:amine range of from 1:1 to 1:3.
  • the added amount of the porogen is suitably from 1 to 99% to the total weight of the epoxy compound, the amine and the porogen.
  • the monolith separation medium of the present invention is useful as a stationary phase for liquid chromatograpy which demonstrates unprecedentedly high performance because the skeletal phase thereof has an average diameter of submicron to micrometer size, and has a non-particle-aggregation-type co-continuous structure, and is constituted of an addition polymer from an epoxy compound of bi- or higher functionality and an amine compound of bi- or higher functionality, and is enriched in an organic matter, and does not contain any carbon atoms derived from aromatic series. Moreover, it can be used for columns of general-purpose size as well as for capillary columns.
  • Columns for separation which are made of this separation medium can be configured to have a theoretical plate number of 50,000 or more per meter of column length.
  • the production process of the present invention can be used effectively for columns having relatively large diameters as well as capillary columns because it is an extremely convenient technique in which an epoxy compound and an amine compound are heated in a porogen to polymerize.
  • the separation medium of the present invention in which a non-particle-aggregation-type and high-performance polymer monolith is formed is produced from a specific combination of an epoxy compound and a hardener to be used as raw materials.
  • the epoxy compound is a non-aromatic epoxy compound of bi- or higher functionality and the hardener be a non-aromatic amine compound.
  • 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate is preferred as the non-aromatic epoxy compound (e.g., TEPIC, which is a commercial name of Nissan Chemistry Industries, Ltd.).
  • TEPIC which is a commercial name of Nissan Chemistry Industries, Ltd.
  • a combination thereof with an amine compound of bi- or higher functionality is preferable because it results in a high-performance polymer monolith separation medium with a non-particle-aggregation-type and three-dimensionally branched structure.
  • An epoxy compound provided as an example is 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate, which may be either a racemic mixture or an optically active substance.
  • TPIC-S 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate
  • BALM bis(4-aminocyclohexyl)methane
  • PEG200 polyethylene glycol having a molecular weight of 200
  • FIG. 1 A scanning electron micrograph of the organic polymer monolith capillary column produced by the above-descried polymerization is shown in FIG. 1 . It is shown that the skeletal phase of this monolith has an average diameter of submicron size and has a non-particle-aggregation-type co-continuous structure, and that a pore formed by the skeletal phase has a three-dimensional network.
  • FIG. 2 A separation chromatogram of uracil and alkylbenzenes obtained by use of the organic polymer monolith capillary column (100 in inner diameter and 21.5 cm in length) of the present invention produced above is shown in FIG. 2 .
  • the alkylbenzenes range from benzene, whose substituent has zero carbon atoms, to hexylbenzene, whose substituent has six carbon atoms.
  • the mobile phase was a 60% aqueous acetonitrile solution, which was adjusted to pH 7.0 with 20 mM phosphate buffer, and the column temperature was room temperature. The detection was conducted by ultraviolet absorption at 210 nm.
  • N in FIG. 2 denotes the theoretical plate number, and indicates, from the top, uracil, benzene and alkylbenzenes. The lower an alkylbenzene is placed, the more carbon atoms its substituent has.
  • t r denotes a retention time and W 0.5h denotes a half-value width.
  • An optically active SSS-isomer of 2,2,2-tri-(2,3-epoxypropyl)-isocyanurate (TEPIC-S) in an amount of 0.40 g as an epoxy compound, 0.63 g of an optically active isomer, (1S,2S)-(+)-1,2-cyclohexanediamine, and 10 g of polyethylene glycol having a molecular weight 300 (PEG300) were mixed, heated and stirred into a state where they were dissolved. Thereafter, they were filled into a fused quartz capillary tube, and heated for 4 hours in an oven at 120° C. to be polymerized.
  • Example 2 The organic polymer monolith of Example 2 produced by the above-mentioned polymerization was also a skeletal phase similar to that of the example 1.
  • FIG. 3 A separation chromatogram of optical antipodes (R, S)-1,1′-bis-2-naphtol obtained by use of the organic polymer monolith capillary column (100 ⁇ m in inner diameter and 17.5 cm in length) of the present invention produced above is shown in FIG. 3 .
  • the mobile phase was a 60% aqueous acetonitrile solution, which was adjusted to pH 7.0 with 20 mM phosphate buffer.
  • the column temperature was adjusted to 28° C., the flow rate of the mobile phase to 0.6 ⁇ L/min (L means liter), the line speed to 0.86 mm/sec, the pressure to 112 kg/cm 2 , and the sample was adjusted to a concentration of 1 mg/mL and 1 ⁇ L of the sample was injected.
  • the detection was conducted at a position 9 cm away from the column by ultraviolet absorption at 210 nm.
  • An aromatic compound (2-[(4-(1-methyl-1-[4-(2oxiranylmethoxy)phenyl]ethyl) phenoxy)met hyl]oxirane: BADE) was used as epoxy compound.
  • an amine compound and a porogen BACM and PEG200 were used as the amine compound and as the porogen, respectively, in the same manner as in the example 1.
  • BACM 0.52 g was dissolved in 7.20 g of PEG200 on heating and then 2.33 g of BADE was added, mixed and stirred. The solution was filled into a fused quartz capillary tube, and heated for 1 hour in an oven at 120° C. to be polymerized.
  • FIG. 4 A separation chromatogram of uracil and benzene obtained by use of the organic polymer monolith capillary column (100 ⁇ m in inner diameter and 20 cm in length) of the comparative example produced above is shown in FIG. 4 .
  • the mobile phase was a 60% aqueous acetonitrile solution, which was adjusted to pH 7.0 with 20 mM phosphate buffer.
  • the column temperature was adjusted to room temperature, the flow rate of the mobile phase to 0.15 mL/min, the line speed to 1.01 mm/sec, and the pressure to 50 kg/cm 2 .
  • the detection was conducted with a capillary having an inner diameter of 50 ⁇ m placed at a position 9 cm away from the column, by ultraviolet absorption at 210 nm.
  • the earlier peak corresponds to uracil and the latter peak corresponds to benzene.
  • the theoretical plate number determined by the half-value width method is 3,085 for uracil and 378 for benzene, which are not more than 1/10 in comparison to that obtained in the example 1 of the present invention.
  • the monolith separation medium of the present invention can be used as a stationary phase for liquid chromatography, even for general-purpose size columns as well as for capillary columns.
  • FIG. 1 A first figure.

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  • Physics & Mathematics (AREA)
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  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
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US8252595B2 (en) 2008-05-13 2012-08-28 University Of Kansas Metal abstraction peptide (MAP) tag and associated methods
US9187735B2 (en) 2012-06-01 2015-11-17 University Of Kansas Metal abstraction peptide with superoxide dismutase activity
EP3335789A4 (en) * 2015-08-10 2018-07-18 Mitsubishi Chemical Corporation Separating agent and liquid-chromatography column

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009050801A1 (ja) * 2007-10-17 2009-04-23 Shimadzu Corporation クロマトグラフィー用モノリス分離媒体及びその製造方法
JP5616586B2 (ja) * 2009-03-12 2014-10-29 地方独立行政法人 大阪市立工業研究所 カラムリアクター
JP5590682B2 (ja) * 2009-08-10 2014-09-17 国立大学法人東北大学 エポキシ樹脂硬化物多孔体、水質保持材、抗菌材及びエポキシ樹脂硬化物多孔体の製造方法
CN106769243B (zh) * 2016-12-19 2023-05-16 广电计量检测（成都）有限公司 一种胺采样管及其制作方法及其使用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265745A (en) * 1977-05-25 1981-05-05 Teijin Limited Permselective membrane
US5453185A (en) * 1991-10-21 1995-09-26 Cornell Research Foundation, Inc. Column with macroporous polymer media

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004070789A2 (en) * 2003-02-03 2004-08-19 The Regent Of The University Of California Rewritable nano-surface organic electrical bistable devices
JP2004264045A (ja) * 2003-02-03 2004-09-24 Japan Organo Co Ltd イオンクロマトグラフィー装置用カラム、サプレッサー及びイオンクロマトグラフィー装置
WO2006073173A1 (ja) * 2005-01-07 2006-07-13 Asahi Kasei Kabushiki Kaisha エポキシ樹脂硬化物多孔体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265745A (en) * 1977-05-25 1981-05-05 Teijin Limited Permselective membrane
US5453185A (en) * 1991-10-21 1995-09-26 Cornell Research Foundation, Inc. Column with macroporous polymer media

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8252595B2 (en) 2008-05-13 2012-08-28 University Of Kansas Metal abstraction peptide (MAP) tag and associated methods
US8278111B2 (en) 2008-05-13 2012-10-02 University Of Kansas Metal abstraction peptide (MAP) tag and associated methods
US8975082B2 (en) 2008-05-13 2015-03-10 University Of Kansas Metal abstraction peptide (MAP) tag and associated methods
US9096652B2 (en) 2008-05-13 2015-08-04 University Of Kansas Metal abstraction peptide (MAP) tag and associated methods
US9187735B2 (en) 2012-06-01 2015-11-17 University Of Kansas Metal abstraction peptide with superoxide dismutase activity
EP3335789A4 (en) * 2015-08-10 2018-07-18 Mitsubishi Chemical Corporation Separating agent and liquid-chromatography column
US10773241B2 (en) 2015-08-10 2020-09-15 Mitsubishi Chemical Corporation Separating medium and column for liquid chromatography

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