US20110210057A1 - Multicapillary column for chromatography and sample preparation - Google Patents
Multicapillary column for chromatography and sample preparation Download PDFInfo
- Publication number
- US20110210057A1 US20110210057A1 US13/105,833 US201113105833A US2011210057A1 US 20110210057 A1 US20110210057 A1 US 20110210057A1 US 201113105833 A US201113105833 A US 201113105833A US 2011210057 A1 US2011210057 A1 US 2011210057A1
- Authority
- US
- United States
- Prior art keywords
- capillary tubes
- stationary phase
- column
- multicapillary
- sample
- 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.)
- Abandoned
Links
Images
Classifications
-
- 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
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
- G01N30/6043—Construction of the column joining multiple columns in parallel
-
- 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
- G01N30/56—Packing methods or coating methods
-
- 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
- G01N30/56—Packing methods or coating methods
- G01N2030/567—Packing methods or coating methods coating
-
- 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
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
- G01N30/6073—Construction of the column body in open tubular form
- G01N30/6078—Capillaries
Definitions
- the present invention relates to a multicapillary column especially useful for liquid chromatography and sample preparation. More particularly, the invention relates to a multicapillary column comprising a plurality of uniform capillaries coated with an insoluble stationary phase, wherein the thickness of the stationary phase is correlated with the radius of the individual capillaries.
- Chromatography is the primary technique for separating complicated mixtures of chemical compounds. This is achieved by passing a sample in a mobile phase through a column containing a stationary phase. Chromatography is distinguished into two branches—gas chromatography (“GC”) and liquid chromatography (“LC”), depending on the physical state of the mobile phase. Two types of columns may be used in both gas and liquid chromatography—packed and capillary. Packed columns consist of a tube filled with packing material. The stationary phase is applied to the surface of the packing material. In capillary columns, the stationary phase is applied directly onto the inner wall of the capillary. Capillary columns offer substantial advantages over packed columns.
- GC gas chromatography
- LC liquid chromatography
- Capillary columns for gas chromatography are made from single wide capillaries (about 0.5 mm inner diameter) compatible with standard chromatographic equipment. The columns are further differentiated based on the number of capillaries contained therein. Monocapillary columns consist of a single tube, while multicapillary columns comprise many tubes, allowing for a high sample capacity.
- liquids are much more viscous.
- the diffusion of molecules in liquids is 10,000-100,000 times slower than in gases.
- the diameter of capillary columns used for liquid chromatography must be very small, usually less than 20 ⁇ m. Due to their minuscule sizes and very low sample capacity, to capillary columns for liquid chromatography made from single capillaries are not compatible with standard equipment and cannot be used for routine liquid chromatography analyses.
- the invention is a highly efficient multicapillary column especially useful for liquid chromatography and sample preparation.
- the column contains a plurality of uniform capillaries that are coated with an insoluble stationary phase.
- the thickness of the stationary phase is correlated with the radius of the individual capillaries for high efficiency.
- Another embodiment of the invention is a method of making a multicapillary column for use in chromatography and sample preparation.
- the multicapillary column is filled with a stationary phase solution.
- the stationary phase solution is then moved toward the end of the column.
- the column is slowly moved in a heated zone or vacuum to facilitate evaporation of the solvent.
- the stationary phase is cross-linked and/or chemically bonded to the walls of the capillaries, rendering the stationary phase insoluble in the mobile phases.
- FIG. 1A is a perspective view of a multicapillary chromatography column according to an embodiment of the present invention, the individual capillaries of which are shown in FIG. 1B (cross section);
- FIG. 2 shows diagrammatically a scheme for deposition of the stationary phase in a multicapillary chromatography column according to an embodiment of the present invention
- FIG. 3 shows perspective views of different sized multicapillary columns used for HPLC applications and sample preparation
- FIG. 4 is a chromatogram showing the separation of a uracil, fluorene, phenanthrene mixture in a multicapillary column according to the present invention
- FIGS. 5A and 5B are the mass-spectra demonstrating the performance of a multicapillary column in desalting and fractionating of complex peptide mixtures
- FIG. 6A is a chromatogram showing the performance of a multicapillary chromatography column in sample enrichment
- FIG. 6B provides a comparison, showing the performance of an SPE cartridge in sample enrichment
- FIG. 7 shows diagrammatically a multicapillary chromatography column for head space analysis of an aqueous sample containing volatiles, according to an embodiment of the present invention.
- FIG. 8 is a comparative table showing the performance of a conventional solid phase extraction cartridge versus a multicapillary chromatography column according to an embodiment of the present invention.
- the present invention describes a highly efficient multicapillary column that is especially useful for liquid chromatography.
- the multicapillary column is also useful for applications such as gas chromatography, supercritical chromatography, electrochromatography, capillary electrophoresis, solid phase extraction, head space analysis, sample concentration, and sample desalting.
- the multicapillary column 10 comprises a rod pierced with a plurality of uniform capillary tubes that receive a sample in a mobile phase at a first end of the column 10 and discharge a separated sample at a second end of the column.
- the interior of each capillary tube is coated with an insoluble stationary phase, wherein the thickness of the stationary phase is correlated with the radius of the individual capillary tubes.
- FIG. 2 there is shown a method for preparing the multicapillary column 10 of the present invention.
- the method comprises introducing a stationary phase solution into a multicapillary column using, for example, pump means.
- a heated zone e.g. an oven
- vacuum or other environment that facilitates evaporation of the solvent. Due to the higher velocity of the solution in wider capillaries, the film of the stationary phase that is deposited on the wider capillaries is thicker than the film that is deposited on the more narrow capillaries.
- the stationary phase is cross-linked and/or chemically bonded to the interior walls of the capillaries.
- the process of the present invention renders the stationary phase material insoluble in the mobile phase (e.g. organic and water-organic solvents).
- the tubes and rods employed herein include, for example, glass, fused silica, metal (e.g. stainless steel) and plastic (e.g. PEEK polymer).
- metal e.g. stainless steel
- plastic e.g. PEEK polymer
- the multicapillary column 10 can be used with capillary tubes of varying dimensions.
- the inner diameter of the capillary tubes may range from about 0.1 ⁇ m to about 100 ⁇ m.
- the outer diameter of the column 10 may range from about 0.1 mm to about 1 m, while the length of the column may range from about 0.1 mm to about 2 m.
- the inventors have correlated the thickness of the stationary phase with the radius of the individual capillaries. During application of the stationary phase, a greater amount settles on the inner surface of wider capillaries. Conversely, a smaller amount settles on the inner surface of narrower capillaries. As a result, the capillaries achieve quasi-uniformity, and the efficiency of the multicapillary column 10 is substantially increased.
- the following relationship for high peak efficiency has been derived by the inventors:
- the stationary phase film thickness d f is proportional to capillary radius r in power n, where n>1; C f is a constant.
- the stationary phase thickness d f should be proportional to capillary radius r in power 3.
- soluble stationary phases e.g. polydimethylsiloxane
- soluble stationary phases cannot be used in liquid chromatography. These phases would simply be washed away with the stream of a mobile phase. Stationary phases for liquid chromatography must be insoluble in the mobile phase.
- the present invention exploits the correlation between the thickness of the stationary phase and the radius of individual capillaries for the preparation of multicapillary columns 10 having insoluble stationary phases appropriate for liquid chromatography.
- the experimental approach used in a method according to the invention involves three steps:
- a 10% solution of vinyldimethylethoxysilane in toluene is pumped at 50 ⁇ L/min for six hours through a clean and dry 1.1 mm outer diameter ⁇ 100 mm multicapillary glass rod pierced with approximately 4,000 capillaries of 10 ⁇ m diameter at 105° C.
- the column is rinsed with toluene, acetone, and methanol and dried with a nitrogen stream.
- the multicapillary column prepared as described in Example 1, is filled with a solution consisting of 100 mg polybutadiene (M.W. 3,400) and 0.5 mg dicumyl peroxide in 100 ml, pentane. While pumping the solution at 5 ⁇ L/min, the opposite end of the column is placed inside an oven heated to 150° C., and the column is moved at a linear speed of 0.5 mm/min ( FIG. 2 ).
- the multicapillary column prepared as described in Example 2, under slow nitrogen flow, is heated at 200° C. for four hours.
- Multicapillary columns containing poly(ethylene glycol), linear and cross-linked polystyrene, and cross-linked polydimethylsiloxane are also prepared.
- the 10% solution of octadecyltriethoxysilane in toluene is pumped at 10 ⁇ L/min for six hours through a clean and dry 2.3 mm outer diameter ⁇ 300 mm multicapillary glass rod pierced with approximately 4,000 capillaries of 20 ⁇ m diameter at 105° C. While pumping the solution, the opposite end of the multicapillary column is moved at a linear speed of 0.5 mm/min inside the oven heated to 150° C. The column is rinsed with toluene, acetone, and methanol and dried with a nitrogen stream.
- a 10% solution of phenyltrimethoxysilane in toluene is used to prepare the stationary phase with phenyl groups.
- a 10% solution of 3-aminopropyltrimethoxysilane in toluene is used to prepare the stationary phase with amino groups.
- a 10% solution of (3-glycidoxypropyl)trimethoxysilane in toluene is used to prepare the stationary phase with glycido groups.
- a 10% solution of N-trimethoxysilylpropyl-N,N,N trimethylammonium chloride in methanol is used to prepare an anion-exchange stationary phase.
- a 10% solution of 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane in toluene is used to prepare a cation-exchange stationary phase.
- a solution containing 1.5% trypsin and 0.4 M dicyclohexylcarbodiimide in 7.5 M urea (pH 4.74 with HCl) is pumped through the multicapillary column functionalized with aminopropyl groups, as described in Example 4, at 50 ⁇ L/min for one hour.
- the multicapillary column is washed with a 7.5 M solution of urea and water.
- the (uracil+fluorene+phenanthrene) mixture is separated on the multicapillary column 10 installed in a Shimadzu HPLC instrument using standard HPLC fittings ( FIG. 3 ).
- the chromatographic conditions and chromatogram are shown reproduced in FIG. 4 .
- the chromatogram shows the uracil peak at about 1.8 minutes, the fluorene peak at about 2.1 minutes, and the phenanthrene peak at about 2.4 minutes.
- the example illustrates an HPLC application using the multicapillary column of the present invention, wherein a typical organic mixture can be analyzed in less than three minutes.
- a 3 ⁇ L volume of the 100 pmole/ ⁇ L peptide mixture obtained by the enzymatic hydrolysis of bovine serum albumin is introduced in a 10 cm long C-18 column prepared as described in Example 4.
- the sample is eluted at 100 ⁇ L/min at room temperature with 100 ⁇ L of deionized water followed by 30 ⁇ L of 40% acetonitrile/water.
- Ten 3 ⁇ L 40% acetonitrile/water fractions are collected and analyzed by atmospheric pressure matrix-assisted laser desorption/ionization mass-spectrometry (“MALDI”). Mass-spectra of Fractions 3 and 6 are shown in FIG. 5 .
- MALDI atmospheric pressure matrix-assisted laser desorption/ionization mass-spectrometry
- This example illustrates the fractionating ability of the multicapillary column of the present invention, prior to mass-spectrometric analysis of a complex peptide mixture.
- FIG. 6 the 2.3 mm outer diameter ⁇ 100 mm length multicapillary C-18 column containing approximately 1,000 capillaries of 40 ⁇ m diameter prepared as described in Example 4 is used for sample enrichment prior to HPLC and GC analyses.
- Very short HPLC columns known as solid phase extraction (“SPE”) cartridges are currently used.
- SPE solid phase extraction
- FIGS. 6A-B and FIG. 8 demonstrate a comparison of the multicapillary column of the present invention versus an SPE cartridge.
- the example clearly demonstrates that the multicapillary column of the present invention can effectively replace an SPE cartridge in sample preparation.
- the 2.3 mm outer diameter ⁇ 100 mm length multicapillary column containing approximately 4,000 capillaries of 20 ⁇ m diameter C-18 column prepared as described in Example 4 for head space sample enrichment prior to gas chromatographic analysis is schematically shown in FIG. 7 .
- a regular 100 ⁇ L HPLC syringe is used to push and pull the air through the multicapillary column about five times.
- Organic volatile compounds above the liquid are adsorbed into the multicapillary column.
- the multicapillary column is removed and eluted with 100 ⁇ L of methanol.
- the methanol extract is analyzed by gas chromatography for the detection of volatile solvents.
- Examples 1-9 demonstrate the wide scope application of the multicapillary column 10 according to the present invention. Accordingly, it can be seen that the multicapillary column is a highly efficient column that has a high sample capacity and is compatible with existing chromatographic equipment. While the multicapillary column 10 is particularly useful for liquid chromatographic applications (e.g., HPLC analysis), the column can be used in a number of related applications without departing from the scope of the invention. These include, but are not limited to, gas chromatography, supercritical chromatography, electrochromatography, capillary electrophoresis, solid phase extraction, head space analysis, sample concentration, and sample desalting.
Abstract
A multicapillary column especially useful for liquid chromatography and sample preparation comprising a plurality of uniform capillaries coated with an insoluble stationary phase, wherein the thickness of the stationary phase is correlated with the radius of the individual capillaries for high efficiency.
Description
- This application is a Continuation of allowed U.S. patent application Ser. No. 11/633,713 filed Dec. 5, 2006, which is a Divisional of U.S. patent application Ser. No. 10/955,377 filed Sep. 30, 2004, now U.S. Pat. No. 7,166,212, which claims priority to U.S. Provisional Patent Application No. 60/507,474 filed Sep. 30, 2003.
- 1. Field of the Invention
- The present invention relates to a multicapillary column especially useful for liquid chromatography and sample preparation. More particularly, the invention relates to a multicapillary column comprising a plurality of uniform capillaries coated with an insoluble stationary phase, wherein the thickness of the stationary phase is correlated with the radius of the individual capillaries.
- 2. Background Art
- Chromatography is the primary technique for separating complicated mixtures of chemical compounds. This is achieved by passing a sample in a mobile phase through a column containing a stationary phase. Chromatography is distinguished into two branches—gas chromatography (“GC”) and liquid chromatography (“LC”), depending on the physical state of the mobile phase. Two types of columns may be used in both gas and liquid chromatography—packed and capillary. Packed columns consist of a tube filled with packing material. The stationary phase is applied to the surface of the packing material. In capillary columns, the stationary phase is applied directly onto the inner wall of the capillary. Capillary columns offer substantial advantages over packed columns.
- In gas chromatography, the vast majority of analyses are conducted using capillary columns Capillary columns for gas chromatography are made from single wide capillaries (about 0.5 mm inner diameter) compatible with standard chromatographic equipment. The columns are further differentiated based on the number of capillaries contained therein. Monocapillary columns consist of a single tube, while multicapillary columns comprise many tubes, allowing for a high sample capacity.
- The diffusion of molecules in gases is very fast, due to the low viscosity.
- Compared to gases, liquids are much more viscous. The diffusion of molecules in liquids is 10,000-100,000 times slower than in gases. To provide rapid mass-transfer, the diameter of capillary columns used for liquid chromatography must be very small, usually less than 20 μm. Due to their minuscule sizes and very low sample capacity, to capillary columns for liquid chromatography made from single capillaries are not compatible with standard equipment and cannot be used for routine liquid chromatography analyses.
- Methods for the preparation of insoluble stationary phases for liquid chromatography are known. Most of these methods are based on chemical bonding of the stationary phases to the surface of chromatographic supports. However, the use of multicapillary columns in liquid chromatographic applications has been constrained because of technical problems. The primary constraint is that the linear flow rate of the mobile phase in wider capillaries is higher than the flow rate in narrower capillaries. If the phase ratio, i.e. the ratio of the radius of the capillary to the stationary phase film thickness, is the same for all capillaries, the sample will move faster in the wider capillaries. As a result, the efficiency of multicapillary columns is always inferior to that of single capillary columns.
- Accordingly, there is a need for an efficient multicapillary column having a high sample capacity, for use in liquid chromatography.
- The invention is a highly efficient multicapillary column especially useful for liquid chromatography and sample preparation. The column contains a plurality of uniform capillaries that are coated with an insoluble stationary phase. The thickness of the stationary phase is correlated with the radius of the individual capillaries for high efficiency.
- Another embodiment of the invention is a method of making a multicapillary column for use in chromatography and sample preparation. In such method, the multicapillary column is filled with a stationary phase solution. The stationary phase solution is then moved toward the end of the column. Simultaneously therewith, the column is slowly moved in a heated zone or vacuum to facilitate evaporation of the solvent. After deposition, the stationary phase is cross-linked and/or chemically bonded to the walls of the capillaries, rendering the stationary phase insoluble in the mobile phases.
-
FIG. 1A is a perspective view of a multicapillary chromatography column according to an embodiment of the present invention, the individual capillaries of which are shown inFIG. 1B (cross section); -
FIG. 2 shows diagrammatically a scheme for deposition of the stationary phase in a multicapillary chromatography column according to an embodiment of the present invention; -
FIG. 3 shows perspective views of different sized multicapillary columns used for HPLC applications and sample preparation; -
FIG. 4 is a chromatogram showing the separation of a uracil, fluorene, phenanthrene mixture in a multicapillary column according to the present invention; -
FIGS. 5A and 5B are the mass-spectra demonstrating the performance of a multicapillary column in desalting and fractionating of complex peptide mixtures; -
FIG. 6A is a chromatogram showing the performance of a multicapillary chromatography column in sample enrichment;FIG. 6B provides a comparison, showing the performance of an SPE cartridge in sample enrichment; -
FIG. 7 shows diagrammatically a multicapillary chromatography column for head space analysis of an aqueous sample containing volatiles, according to an embodiment of the present invention; and -
FIG. 8 is a comparative table showing the performance of a conventional solid phase extraction cartridge versus a multicapillary chromatography column according to an embodiment of the present invention. - The use of multicapillary columns in liquid chromatographic applications has been constrained because of technical problems. The fundamental problem is that the diameter of the capillaries in multicapillary rods is uniform but not identical. As a result, the mobile phase moves faster in wider capillaries than in narrower capillaries. The efficiency of multicapillary columns is therefore inferior to that of single capillary columns. Thus, in order to manufacture high efficiency multicapillary columns, it is critical that an appropriate technique for the deposition of a stationary phase be employed.
- The present invention describes a highly efficient multicapillary column that is especially useful for liquid chromatography. The multicapillary column is also useful for applications such as gas chromatography, supercritical chromatography, electrochromatography, capillary electrophoresis, solid phase extraction, head space analysis, sample concentration, and sample desalting.
- Referring now to
FIG. 1 , there is shown a cross-section of amulticapillary column 10 according to the present invention. Themulticapillary column 10 comprises a rod pierced with a plurality of uniform capillary tubes that receive a sample in a mobile phase at a first end of thecolumn 10 and discharge a separated sample at a second end of the column. The interior of each capillary tube is coated with an insoluble stationary phase, wherein the thickness of the stationary phase is correlated with the radius of the individual capillary tubes. This advantageously ensures that themulticapillary column 10 of the present invention has a substantially higher efficiency than multicapillary columns of the prior art, wherein the thickness of the stationary phase is not correlated with the radius of the capillaries. This improved performance, which derives from the correlation presented herein, makes it possible to employ themulticapillary column 10 as an effective and efficient tool for liquid chromatographic applications. - In
FIG. 2 , there is shown a method for preparing themulticapillary column 10 of the present invention. The method comprises introducing a stationary phase solution into a multicapillary column using, for example, pump means. As the stationary phase solution is moved toward the end of the multicapillary column, the column is simultaneously moved in a heated zone (e.g. an oven), vacuum, or other environment that facilitates evaporation of the solvent. Due to the higher velocity of the solution in wider capillaries, the film of the stationary phase that is deposited on the wider capillaries is thicker than the film that is deposited on the more narrow capillaries. After deposition, the stationary phase is cross-linked and/or chemically bonded to the interior walls of the capillaries. The process of the present invention renders the stationary phase material insoluble in the mobile phase (e.g. organic and water-organic solvents). - By varying the thickness of the stationary phase in the individual capillaries, there is obtained a
column 10 having high efficiency in liquid chromatographic applications. - Preferred materials for the fabrication of the tubes and rods employed herein include, for example, glass, fused silica, metal (e.g. stainless steel) and plastic (e.g. PEEK polymer). For liquid chromatographic applications, it is often desirable to employ a large number of capillary tubes (e.g. thousands), however, any number of capillary tubes may be employed in the
multicapillary column 10 of the present invention. It will also be understood that themulticapillary column 10 can be used with capillary tubes of varying dimensions. For example, the inner diameter of the capillary tubes may range from about 0.1 μm to about 100 μm. The outer diameter of thecolumn 10 may range from about 0.1 mm to about 1 m, while the length of the column may range from about 0.1 mm to about 2 m. - The important relationship between the stationary phase thickness and capillary radius will now be discussed in further detail:
- According to Poiseuille's law, the mobile phase velocity in wider capillaries is faster than its velocity in more narrow capillaries. As a result, a sample is eluted from a multicapillary column in the form of a broad peak. This phenomenon is known as peak broadening.
- To solve this problem, that is, to optimize the chromatographic efficiency of multicapillary columns, the inventors have correlated the thickness of the stationary phase with the radius of the individual capillaries. During application of the stationary phase, a greater amount settles on the inner surface of wider capillaries. Conversely, a smaller amount settles on the inner surface of narrower capillaries. As a result, the capillaries achieve quasi-uniformity, and the efficiency of the
multicapillary column 10 is substantially increased. The following relationship for high peak efficiency has been derived by the inventors: -
d f(r)=c f ·r n (Equation 1) - The stationary phase film thickness df is proportional to capillary radius r in power n, where n>1; Cf is a constant.
- To achieve the highest peak efficiency, the stationary phase thickness df should be proportional to capillary radius r in
power 3. - For gas chromatographic applications, the foregoing relationship is used to deposit soluble stationary phases (e.g. polydimethylsiloxane) on the surface of multicapillary columns. However, soluble stationary phases cannot be used in liquid chromatography. These phases would simply be washed away with the stream of a mobile phase. Stationary phases for liquid chromatography must be insoluble in the mobile phase.
- The present invention exploits the correlation between the thickness of the stationary phase and the radius of individual capillaries for the preparation of
multicapillary columns 10 having insoluble stationary phases appropriate for liquid chromatography. The experimental approach used in a method according to the invention involves three steps: - I. Chemical modification of the capillary walls with organosilicon compounds containing double bonds, such as, for example, vinyldimethylethoxysilane. The reaction scheme is illustrated below:
-
Surface-OH+EtO—SiMe2-CH═CH2→Surface-O—SiMe2-CH═CH2+EtOH - II. Deposition of a soluble stationary phase containing residual double bonds on the surface of capillaries to correlate film thickness with the capillary radius. A representative example of such stationary phase is polybutadiene. A scheme for the physical deposition of linear polybutadiene is shown below (see
FIG. 2 ): -
Surface-O—SiMe2-CH═CH2+Polybutadiene in solution→Surface-O—SiMe2-CH═CH2/Polybutadiene on surface - III. Immobilization of the stationary phase by cross-linking and bonding it to the capillary walls. This process is based on reactions between the residual double bonds of the stationary phase and double bonds located on the surface of the capillaries. The reaction is conducted at elevated temperatures in the presence of polymerization initiators. This step can be illustrated as follows:
-
Surface-O—SiMe2-CH═CH2/Polybutadiene on surface→Surface-O—SiMe2-CH2-CH2-Polybutadiene (cross-linked, bonded, and insoluble) - A 10% solution of vinyldimethylethoxysilane in toluene is pumped at 50 μL/min for six hours through a clean and dry 1.1 mm outer diameter×100 mm multicapillary glass rod pierced with approximately 4,000 capillaries of 10 μm diameter at 105° C. The column is rinsed with toluene, acetone, and methanol and dried with a nitrogen stream.
- The multicapillary column, prepared as described in Example 1, is filled with a solution consisting of 100 mg polybutadiene (M.W. 3,400) and 0.5 mg dicumyl peroxide in 100 ml, pentane. While pumping the solution at 5 μL/min, the opposite end of the column is placed inside an oven heated to 150° C., and the column is moved at a linear speed of 0.5 mm/min (
FIG. 2 ). - The multicapillary column, prepared as described in Example 2, under slow nitrogen flow, is heated at 200° C. for four hours. Multicapillary columns containing poly(ethylene glycol), linear and cross-linked polystyrene, and cross-linked polydimethylsiloxane are also prepared.
- The 10% solution of octadecyltriethoxysilane in toluene is pumped at 10 μL/min for six hours through a clean and dry 2.3 mm outer diameter×300 mm multicapillary glass rod pierced with approximately 4,000 capillaries of 20 μm diameter at 105° C. While pumping the solution, the opposite end of the multicapillary column is moved at a linear speed of 0.5 mm/min inside the oven heated to 150° C. The column is rinsed with toluene, acetone, and methanol and dried with a nitrogen stream.
- A 10% solution of phenyltrimethoxysilane in toluene is used to prepare the stationary phase with phenyl groups. A 10% solution of 3-aminopropyltrimethoxysilane in toluene is used to prepare the stationary phase with amino groups. A 10% solution of (3-glycidoxypropyl)trimethoxysilane in toluene is used to prepare the stationary phase with glycido groups. A 10% solution of N-trimethoxysilylpropyl-N,N,N trimethylammonium chloride in methanol is used to prepare an anion-exchange stationary phase. A 10% solution of 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane in toluene is used to prepare a cation-exchange stationary phase.
- A solution containing 1.5% trypsin and 0.4 M dicyclohexylcarbodiimide in 7.5 M urea (pH 4.74 with HCl) is pumped through the multicapillary column functionalized with aminopropyl groups, as described in Example 4, at 50 μL/min for one hour. The multicapillary column is washed with a 7.5 M solution of urea and water.
- A similar procedure is used for the immobilization of avidin, pepsin, and ovalbumin.
- Referring now to
FIG. 4 , the (uracil+fluorene+phenanthrene) mixture is separated on themulticapillary column 10 installed in a Shimadzu HPLC instrument using standard HPLC fittings (FIG. 3 ). The chromatographic conditions and chromatogram are shown reproduced inFIG. 4 . The chromatogram shows the uracil peak at about 1.8 minutes, the fluorene peak at about 2.1 minutes, and the phenanthrene peak at about 2.4 minutes. - The example illustrates an HPLC application using the multicapillary column of the present invention, wherein a typical organic mixture can be analyzed in less than three minutes.
- Referring to
FIG. 5 , a 3 μL volume of the 100 pmole/μL peptide mixture obtained by the enzymatic hydrolysis of bovine serum albumin is introduced in a 10 cm long C-18 column prepared as described in Example 4. The sample is eluted at 100 μL/min at room temperature with 100 μL of deionized water followed by 30 μL of 40% acetonitrile/water. Ten 3 μL 40% acetonitrile/water fractions are collected and analyzed by atmospheric pressure matrix-assisted laser desorption/ionization mass-spectrometry (“MALDI”). Mass-spectra ofFractions FIG. 5 . - This example illustrates the fractionating ability of the multicapillary column of the present invention, prior to mass-spectrometric analysis of a complex peptide mixture.
- Referring to
FIG. 6 , the 2.3 mm outer diameter×100 mm length multicapillary C-18 column containing approximately 1,000 capillaries of 40 μm diameter prepared as described in Example 4 is used for sample enrichment prior to HPLC and GC analyses. Very short HPLC columns known as solid phase extraction (“SPE”) cartridges are currently used. Compared to SPE cartridges, multicapillary columns are much faster, simpler and reusable.FIGS. 6A-B andFIG. 8 demonstrate a comparison of the multicapillary column of the present invention versus an SPE cartridge. - The example clearly demonstrates that the multicapillary column of the present invention can effectively replace an SPE cartridge in sample preparation.
- The 2.3 mm outer diameter×100 mm length multicapillary column containing approximately 4,000 capillaries of 20 μm diameter C-18 column prepared as described in Example 4 for head space sample enrichment prior to gas chromatographic analysis is schematically shown in
FIG. 7 . A regular 100 μL HPLC syringe is used to push and pull the air through the multicapillary column about five times. Organic volatile compounds above the liquid are adsorbed into the multicapillary column. After this adsorption step, the multicapillary column is removed and eluted with 100 μL of methanol. The methanol extract is analyzed by gas chromatography for the detection of volatile solvents. - This example demonstrates that as compared to conventional methods of head-space analysis, the multicapillary column of the present invention is an easier, faster and simpler alternative.
- Examples 1-9 demonstrate the wide scope application of the
multicapillary column 10 according to the present invention. Accordingly, it can be seen that the multicapillary column is a highly efficient column that has a high sample capacity and is compatible with existing chromatographic equipment. While themulticapillary column 10 is particularly useful for liquid chromatographic applications (e.g., HPLC analysis), the column can be used in a number of related applications without departing from the scope of the invention. These include, but are not limited to, gas chromatography, supercritical chromatography, electrochromatography, capillary electrophoresis, solid phase extraction, head space analysis, sample concentration, and sample desalting. - Specific examples of the above-mentioned applications include, for example: liquid chromatographic separation of organic compounds, fractionating complicated mixtures prior to instrumental analysis, fractionating peptide mixtures prior to mass-spectrometric analysis, desalting samples prior to instrumental analysis, desalting peptide solutions, desalting protein solutions, sample concentrating prior to instrumental analysis, peptide concentrating prior to mass-spectrometric analysis, and head space concentrating of volatile samples.
- While the invention has been particularly shown and described with reference to the examples and preferred embodiments thereof, it will be understood by those skilled in the art that various alterations in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (4)
1. A multicapillary column, especially useful for liquid chromatography and sample preparation applications, comprising:
(a) a plurality of capillary tubes contained within a column for receiving a sample at a first end of the column and discharging a separated sample at a second end of the column;
(b) an insoluble stationary phase being coated directly on interior surfaces of said capillary tubes; said stationary phase coating comprising a thickness that is correlated with the radius of individual capillary tubes for achieving high efficiency capillary tubes by applying a greater amount of stationary phase on wider capillary tubes and a lesser amount of stationary phase on narrower capillary tubes to enhance uniformity of said capillary tubes; and
wherein the insoluble stationary phase coating additionally contains peptide moieties.
2. A multicapillary column, especially useful for liquid chromatography and sample preparation applications, comprising:
(a) a plurality of capillary tubes contained within a column for receiving a sample at a first end of the column and discharging a separated sample at a second end of the column;
(b) an insoluble stationary phase being coated directly on interior surfaces of said capillary tubes; said stationary phase coating comprising a thickness that is correlated with the radius of individual capillary tubes for achieving high efficiency capillary tubes by applying a greater amount of stationary phase on wider capillary tubes and a lesser amount of stationary phase on narrower capillary tubes to enhance uniformity of said capillary tubes; and
wherein the stationary phase coating additionally contains macrocyclic glycopeptide moieties.
3. A multicapillary column, especially useful for liquid chromatography and sample preparation applications, comprising:
(a) a plurality of capillary tubes contained within a column for receiving a sample at a first end of the column and discharging a separated sample at a second end of the column;
(b) an insoluble stationary phase being coated directly on interior surfaces of said capillary tubes; said stationary phase coating comprising a thickness that is correlated with the radius of individual capillary tubes for achieving high efficiency capillary tubes by applying a greater amount of stationary phase on wider capillary tubes and a lesser amount of stationary phase on narrower capillary tubes to enhance uniformity of said capillary tubes; and
wherein the stationary phase coating additionally contains protein moieties.
4. A multicapillary column, especially useful for liquid chromatography and sample preparation applications, comprising:
(a) a plurality of capillary tubes contained within a column for receiving a sample at a first end of the column and discharging a separated sample at a second end of the column;
(b) an insoluble stationary phase being coated directly on interior surfaces of said capillary tubes; said stationary phase coating comprising a thickness that is correlated with the radius of individual capillary tubes for achieving high efficiency capillary tubes by applying a greater amount of stationary phase on wider capillary tubes and a lesser amount of stationary phase on narrower capillary tubes to enhance uniformity of said capillary tubes; and
wherein the stationary phase coating additionally contains antibody moieties.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/105,833 US20110210057A1 (en) | 2003-09-30 | 2011-05-11 | Multicapillary column for chromatography and sample preparation |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50747403P | 2003-09-30 | 2003-09-30 | |
US10/955,377 US7166212B2 (en) | 2003-09-30 | 2004-09-30 | Multicapillary column for chromatography and sample preparation |
US11/633,713 US7964097B2 (en) | 2003-09-30 | 2006-12-05 | Multicapillary column for chromatography and sample preparation |
US13/105,833 US20110210057A1 (en) | 2003-09-30 | 2011-05-11 | Multicapillary column for chromatography and sample preparation |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/633,713 Continuation US7964097B2 (en) | 2003-09-30 | 2006-12-05 | Multicapillary column for chromatography and sample preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
US20110210057A1 true US20110210057A1 (en) | 2011-09-01 |
Family
ID=34421624
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/955,377 Expired - Fee Related US7166212B2 (en) | 2003-09-30 | 2004-09-30 | Multicapillary column for chromatography and sample preparation |
US11/633,713 Expired - Fee Related US7964097B2 (en) | 2003-09-30 | 2006-12-05 | Multicapillary column for chromatography and sample preparation |
US13/105,833 Abandoned US20110210057A1 (en) | 2003-09-30 | 2011-05-11 | Multicapillary column for chromatography and sample preparation |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/955,377 Expired - Fee Related US7166212B2 (en) | 2003-09-30 | 2004-09-30 | Multicapillary column for chromatography and sample preparation |
US11/633,713 Expired - Fee Related US7964097B2 (en) | 2003-09-30 | 2006-12-05 | Multicapillary column for chromatography and sample preparation |
Country Status (4)
Country | Link |
---|---|
US (3) | US7166212B2 (en) |
EP (1) | EP1677886A1 (en) |
JP (1) | JP2007507721A (en) |
WO (1) | WO2005032688A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8980093B2 (en) | 2003-09-30 | 2015-03-17 | Yuri P. Belov | Multicapillary device for sample preparation |
WO2019042989A1 (en) * | 2017-08-29 | 2019-03-07 | Labomatic Instruments Ag | Tube assembly |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1677886A1 (en) * | 2003-09-30 | 2006-07-12 | Chromba, Inc. | Multicapillary column for chromatography and sample preparation |
US7740763B2 (en) * | 2004-08-10 | 2010-06-22 | Clemson University | Capillary-channeled polymeric fiber as solid phase extraction media |
US20070181479A1 (en) * | 2005-11-21 | 2007-08-09 | Pentax Corporation | Column and method of manufacturing the column |
CN100435935C (en) * | 2006-02-14 | 2008-11-26 | 厦门大学 | Method of preparing octadecyl type integral liquid chromatography micro-column |
DE102006023223B3 (en) * | 2006-05-18 | 2007-11-15 | Bruker Biospin Gmbh | Apparatus for analyzing a liquid sample with a multi-lumen capillary |
AU2006348443A1 (en) * | 2006-09-20 | 2008-03-27 | Chromba, Inc. | Multicapillary device for sample preparation |
EP2503330A3 (en) * | 2006-09-20 | 2013-04-17 | Chromba, Inc. | Multicapillary device for sample preparation |
JP5389659B2 (en) * | 2006-11-07 | 2014-01-15 | ウオーターズ・テクノロジーズ・コーポレイシヨン | Monolith electrokinetic pump manufacturing |
EP2274098B1 (en) * | 2008-03-28 | 2013-12-25 | Biotix, Inc. | Multicapillary sample preparation devices and methods for processing analytes |
JP2011517773A (en) * | 2008-03-28 | 2011-06-16 | バイオティクス, インコーポレイテッド | Sample preparation device and analyte processing method |
US8132443B2 (en) | 2008-05-01 | 2012-03-13 | The United States Of America As Represented By The Secretary Of The Navy | Microfabricated gas chromatograph |
US8117895B2 (en) * | 2008-06-12 | 2012-02-21 | Northern Alberta Institute Of Technology | Gas chromatography capillary devices and methods |
FR2957276A1 (en) | 2010-03-15 | 2011-09-16 | Francois Parmentier | MULTICAPILLARY MONOLITH |
US10041747B2 (en) | 2010-09-22 | 2018-08-07 | Raytheon Company | Heat exchanger with a glass body |
US20140349839A1 (en) | 2011-09-15 | 2014-11-27 | Francois Parmentier | Multi-capillary monolith made from amorphous silica and/or activated alumina |
JP2012123014A (en) * | 2012-02-20 | 2012-06-28 | Chromba Inc | Multiple capillary device for sample preparation |
US10767259B2 (en) | 2013-07-19 | 2020-09-08 | Agilent Technologies, Inc. | Components with an atomic layer deposition coating and methods of producing the same |
US20150024152A1 (en) * | 2013-07-19 | 2015-01-22 | Agilent Technologies, Inc. | Metal components with inert vapor phase coating on internal surfaces |
FR3049874A1 (en) * | 2016-04-06 | 2017-10-13 | Francois Parmentier | CHROMATOGRAPHY PROCESS |
CN106390522B (en) * | 2016-11-11 | 2018-12-28 | 苏州楚博生物技术有限公司 | The chromatographic column of high separating effect |
EP3602035B1 (en) * | 2017-03-20 | 2023-05-10 | Koninklijke Philips N.V. | Gas chromatography column with polybutadiene coating |
CN111615415B (en) * | 2017-10-12 | 2023-03-10 | 弗朗索瓦·帕门蒂尔 | Material exchange method |
US20230313366A1 (en) * | 2020-10-30 | 2023-10-05 | Agilent Technologies, Inc. | Resistive coating for a capillary |
Citations (82)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3570673A (en) * | 1968-09-07 | 1971-03-16 | Jenaer Glaswerk Schott & Gen | Separation column for liquid chromatography |
US4043905A (en) * | 1974-08-26 | 1977-08-23 | Indiana University Foundation | Chromatographic separation columns with selectively modified active surfaces and methods for their preparations |
US4045352A (en) * | 1973-05-23 | 1977-08-30 | California Institute Of Technology | Ion-exchange hollow fibers |
US4214020A (en) * | 1977-11-17 | 1980-07-22 | Monsanto Company | Processes for coating bundles of hollow fiber membranes |
US4293415A (en) * | 1979-04-27 | 1981-10-06 | Hewlett-Packard Company | Silica chromatographic column |
US4293413A (en) * | 1979-12-28 | 1981-10-06 | Baxter Travenol Laboratories, Inc. | Dialyzer blood circuit and bubble traps |
US4424127A (en) * | 1980-03-07 | 1984-01-03 | Johan Roeraade | Column for liquid and gas chromatography |
US4654265A (en) * | 1985-06-05 | 1987-03-31 | Ube Industries, Ltd. | Porous hollow fiber |
US4657742A (en) * | 1985-07-01 | 1987-04-14 | Ppg Industries, Inc. | Packed fiber glass reaction vessel |
US4689267A (en) * | 1984-07-26 | 1987-08-25 | Shin-Etsu Chemical Co., Ltd. | Composite hollow fiber |
US4818264A (en) * | 1987-04-30 | 1989-04-04 | The Dow Chemical Company | Multicapillary gas chromatography column |
US4957620A (en) * | 1988-11-15 | 1990-09-18 | Hoechst Celanese Corporation | Liquid chromatography using microporous hollow fibers |
US4999164A (en) * | 1986-10-20 | 1991-03-12 | Eppendorf-Netheler-Hinz Gmbh | Pipetting device comprising a retaining cone for holding a slip-on pipette tip and pipette tip for such pipetting device |
US5092219A (en) * | 1987-07-08 | 1992-03-03 | Thermedics Inc. | Selective decomposition of nitrite esters and nitramines |
US5154822A (en) * | 1986-07-28 | 1992-10-13 | 3I Research Exploitation Limited | Bonded chromatographic stationary phase |
US5160627A (en) * | 1990-10-17 | 1992-11-03 | Hoechst Celanese Corporation | Process for making microporous membranes having gel-filled pores, and separations methods using such membranes |
US5194333A (en) * | 1989-12-18 | 1993-03-16 | Tosoh Corporation | Packing material for reversed phase chromatography and process for its preparation |
US5395521A (en) * | 1991-05-31 | 1995-03-07 | Board Of Regents, The University Of Texas System | Automated column equilibration, column loading, column washing and column elution |
US5429746A (en) * | 1994-02-22 | 1995-07-04 | Smith Kline Beecham Corporation | Antibody purification |
US5438127A (en) * | 1993-09-27 | 1995-08-01 | Becton Dickinson And Company | DNA purification by solid phase extraction using a PCl3 modified glass fiber membrane |
US5460781A (en) * | 1989-10-27 | 1995-10-24 | Fujirebio Kabushiki Kaisha | Hemoglobin sampler |
US5552047A (en) * | 1994-05-24 | 1996-09-03 | Terumo Kabushiki Kaisha | Hollow filament blood processing apparatus |
US5774779A (en) * | 1996-11-06 | 1998-06-30 | Materials And Electrochemical Research (Mer) Corporation | Multi-channel structures and processes for making such structures |
US5876918A (en) * | 1993-03-08 | 1999-03-02 | Hydros, Inc. | Aligned fiber diagnostic chromatography with positive and negative controls |
US6045757A (en) * | 1997-06-30 | 2000-04-04 | Rainin Instrument Co., Inc. | Membrane filter pipette tip |
US6048457A (en) * | 1997-02-26 | 2000-04-11 | Millipore Corporation | Cast membrane structures for sample preparation |
US6117394A (en) * | 1996-04-10 | 2000-09-12 | Smith; James C. | Membrane filtered pipette tip |
US6123905A (en) * | 1997-01-17 | 2000-09-26 | Matrix Technologies Corporation | Pipettor including an indicator and method of use |
US6168948B1 (en) * | 1995-06-29 | 2001-01-02 | Affymetrix, Inc. | Miniaturized genetic analysis systems and methods |
US6174352B1 (en) * | 1998-11-24 | 2001-01-16 | Uop Llc | Round profile multi-capillary assembly and method of making |
US6174673B1 (en) * | 1997-06-16 | 2001-01-16 | Diversa Corporation | High throughput screening for novel enzymes |
US6207049B1 (en) * | 1999-07-30 | 2001-03-27 | Agilent Technologies, Inc. | Multichannel capillary column |
US6231739B1 (en) * | 1998-09-11 | 2001-05-15 | The Perkin-Elmer Corporation | Multi-channel capillary electrophoresis device including sheath-flow cuvette and replacable capillary array |
US6270674B1 (en) * | 1997-06-14 | 2001-08-07 | Akzo Nobel Nv | Membrane module with unilaterally embedded hollow fiber membranes |
US6306659B1 (en) * | 1996-06-28 | 2001-10-23 | Caliper Technologies Corp. | High throughput screening assay systems in microscale fluidic devices |
US6309828B1 (en) * | 1998-11-18 | 2001-10-30 | Agilent Technologies, Inc. | Method and apparatus for fabricating replicate arrays of nucleic acid molecules |
US6338802B1 (en) * | 1998-10-29 | 2002-01-15 | Pe Corporation (Ny) | Multi-well microfiltration apparatus |
US6357484B1 (en) * | 1998-08-31 | 2002-03-19 | Uop Llc | Microporous structure defined by a multiplicity of singular channels and method of making |
US6387331B1 (en) * | 1998-01-12 | 2002-05-14 | Massachusetts Institute Of Technology | Method and apparatus for performing microassays |
US6406921B1 (en) * | 1998-07-14 | 2002-06-18 | Zyomyx, Incorporated | Protein arrays for high-throughput screening |
US6416716B1 (en) * | 2001-04-20 | 2002-07-09 | Ashok Kumar Shukla | Sample preparation device with embedded separation media |
US20020110495A1 (en) * | 2001-01-05 | 2002-08-15 | Denis Hunt | Devices and methods for purification |
US6451260B1 (en) * | 1997-08-26 | 2002-09-17 | Dyax Corp. | Method for producing microporous elements, the microporous elements thus produced and uses thereof |
US20030007897A1 (en) * | 2001-07-06 | 2003-01-09 | Andrew Creasey | Pipette tips |
US6537502B1 (en) * | 2000-07-25 | 2003-03-25 | Harvard Apparatus, Inc. | Surface coated housing for sample preparation |
US20030068317A1 (en) * | 2001-04-20 | 2003-04-10 | William Lee | High capacity methods for separation, purification, concentration, immobilization and synthesis of compounds and applications based thereupon |
US6566145B2 (en) * | 2000-02-09 | 2003-05-20 | William E Brewer | Disposable pipette extraction |
US6576478B1 (en) * | 1998-07-14 | 2003-06-10 | Zyomyx, Inc. | Microdevices for high-throughput screening of biomolecules |
US6596237B1 (en) * | 1998-04-27 | 2003-07-22 | Nicholas F. Borrelli | Redrawn capillary imaging reservoir |
US20030173284A1 (en) * | 2000-05-13 | 2003-09-18 | Baker Matthew John | Separation device |
US6638482B1 (en) * | 1993-11-01 | 2003-10-28 | Nanogen, Inc. | Reconfigurable detection and analysis apparatus and method |
US20040038316A1 (en) * | 1999-05-10 | 2004-02-26 | Robert Kaiser | Cell separation device and methods for use |
US6759126B1 (en) * | 1998-09-21 | 2004-07-06 | University Of South Florida | Solid phase microextraction fiber structure and method of making |
US20040147042A1 (en) * | 1999-05-28 | 2004-07-29 | Miklos Gratzl | Device for precise chemical delivery and solution preparation |
US6780582B1 (en) * | 1998-07-14 | 2004-08-24 | Zyomyx, Inc. | Arrays of protein-capture agents and methods of use thereof |
US6780314B2 (en) * | 2000-11-01 | 2004-08-24 | Shinwa Chemical Industries, Ltd. | Separation column for chromatography, medium for solid phase extraction and sample injection system for chromatography |
US6794127B1 (en) * | 1997-06-16 | 2004-09-21 | Diversa Corporation | Capillary array-based sample screening |
US20040191537A1 (en) * | 2001-06-13 | 2004-09-30 | Dieter Lubda | Restricted access material for spme |
US20050003211A1 (en) * | 2000-09-05 | 2005-01-06 | Hitachi, Ltd. | Removal method for coating of polymer coated glass capillary tubing and polymer coated glass capillary tubing |
US20050019951A1 (en) * | 2003-07-14 | 2005-01-27 | Gjerde Douglas T. | Method and device for extracting an analyte |
US6870165B2 (en) * | 2001-10-19 | 2005-03-22 | Biocal Technology, Inc. | Multi-color multiplexed analysis in a bio-separation system |
US6886824B2 (en) * | 1998-08-25 | 2005-05-03 | Minolta Co., Ltd. | Binding member removing apparatus, automatic document feeder, sheet processing apparatus, and image forming apparatus |
US20050139536A1 (en) * | 2003-09-30 | 2005-06-30 | Belov Yuri P. | Multicapillary column for chromatography and sample preparation |
US20050178709A1 (en) * | 2004-01-23 | 2005-08-18 | Ngk Insulators, Ltd. | Supports for solid phase extraction |
US6992181B2 (en) * | 1999-10-28 | 2006-01-31 | Gyros Ab | DNA isolation method |
US20060062701A1 (en) * | 2002-07-18 | 2006-03-23 | Hiroyuki Nakamura | Method of manufacturing microwave reaction device and microwave reaction device |
US20060093518A1 (en) * | 2004-10-29 | 2006-05-04 | Shukla Ashok K | Device containing non-covalently bound biomolecules on solid support |
US20060118491A1 (en) * | 2004-12-03 | 2006-06-08 | Gjerde Douglas T | Method and device for desalting an analyte |
US20060201881A1 (en) * | 2004-08-10 | 2006-09-14 | Clemson University | Capillary-channeled polymeric fiber as solid phase extraction media |
US20060216206A1 (en) * | 2003-05-29 | 2006-09-28 | Hudson William C | Solid phase extraction pipette |
US7118657B2 (en) * | 1999-06-22 | 2006-10-10 | President And Fellows Of Harvard College | Pulsed ion beam control of solid state features |
US7118671B2 (en) * | 2003-04-30 | 2006-10-10 | Institute For Roentgen Optics | Polycapillary chromatographic column and method of its manufacturing |
US7122640B2 (en) * | 2002-06-10 | 2006-10-17 | Phynexus, Inc. | Open channel solid phase extraction systems and methods |
US20070017870A1 (en) * | 2003-09-30 | 2007-01-25 | Belov Yuri P | Multicapillary device for sample preparation |
US20070071649A1 (en) * | 2001-09-10 | 2007-03-29 | Marcus R Kenneth | Capillary-channeled polymer fibers as stationary phase media for spectroscopic analysis |
US7208072B2 (en) * | 2002-01-18 | 2007-04-24 | Biocal Technology, Inc. | Multi-segment cartridge for bio-separation with multiplexed fluorescence detection |
US20070111194A1 (en) * | 2003-12-15 | 2007-05-17 | Preentec Ag | Method for the concentration and purification of biological compounds |
US20070116607A1 (en) * | 2005-11-23 | 2007-05-24 | Pharmacom Microlelectronics, Inc. | Microsystems that integrate three-dimensional microarray and multi-layer microfluidics for combinatorial detection of bioagent at single molecule level |
US7247469B2 (en) * | 1998-07-14 | 2007-07-24 | Zyomyx, Inc. | Non-specific binding resistant protein arrays and methods for making the same |
US7271895B2 (en) * | 2004-04-09 | 2007-09-18 | Institute For Roentgen Optics | Fluorescent sensor on basis of multichannel structures |
US20070215543A1 (en) * | 2006-03-14 | 2007-09-20 | Mettler-Toledo Autochem, Inc. | Small volume liquid-liquid extraction device and method of use |
US7276158B1 (en) * | 2000-06-09 | 2007-10-02 | Ashok K Shukla | Incision-based filtration/separation pipette tip |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH654666A5 (en) | 1982-01-21 | 1986-02-28 | Eidgenoess Oberzolldirektion | Separation column for liquid chromatography |
SU1651200A1 (en) | 1986-12-04 | 1991-05-23 | Предприятие П/Я А-1882 | Multiple-capillary chromatographic column |
DE4234728A1 (en) * | 1992-10-15 | 1994-04-21 | Peter Prof Dr Bartholmes | Process for the recovery and the buffering and / or concentration of dissolved macromolecules of a macromolecule mixture |
RU2060498C1 (en) | 1993-01-11 | 1996-05-20 | Институт катализа Сибирского отделения РАН | Chromatographic column |
DE4443754C2 (en) | 1994-12-08 | 1996-09-26 | Daimler Benz Ag | Gas chromatograph |
US5552042A (en) | 1995-02-24 | 1996-09-03 | Uop | Rigid silica capillary assembly |
US6972183B1 (en) | 1997-06-16 | 2005-12-06 | Diversa Corporation | Capillary array-based enzyme screening |
DE19626956B4 (en) * | 1996-07-04 | 2006-10-12 | Wabco Gmbh & Co.Ohg | Gas dryer with an outlet chamber |
RU2114427C1 (en) | 1996-09-27 | 1998-06-27 | Конструкторско-технологический институт геофизического и экологического приборостроения СО РАН | Polycapillary chromatographic column |
US5851491A (en) * | 1997-06-13 | 1998-12-22 | Labcon, North America | Pipette tip and filter for accurate sampling and prevention of contamination |
EP0926492A1 (en) | 1997-12-02 | 1999-06-30 | Uop Llc | Round profile multi-capillary assembly useful in chromatography |
US6007609A (en) * | 1997-12-18 | 1999-12-28 | Uop Llc | Pressurized container with restrictor tube having multiple capillary passages |
US6333088B1 (en) * | 1999-01-13 | 2001-12-25 | Uop Llc | Compound capillary assembly and use in separative transport |
US6143252A (en) * | 1999-04-12 | 2000-11-07 | The Perkin-Elmer Corporation | Pipetting device with pipette tip for solid phase reactions |
US6325114B1 (en) * | 2000-02-01 | 2001-12-04 | Incyte Genomics, Inc. | Pipetting station apparatus |
DE60126336T2 (en) | 2000-12-14 | 2007-11-08 | Dupont Dow Elastomers L.L.C., Wilmington | METHOD FOR PRODUCING HIGH-PURGING PERCUSSIONAL PERIPHERAL OBJECTS |
ATE522802T1 (en) | 2001-01-26 | 2011-09-15 | Qiagen Sciences Llc | MULTI-CHANNEL CASSETTE FOR BIOSEPARATION |
RU2190846C1 (en) | 2001-04-19 | 2002-10-10 | Институт катализа им. Г.К.Борескова СО РАН | Chromatographic polycapillary column |
JP3759910B2 (en) | 2002-02-28 | 2006-03-29 | 日東電工株式会社 | Chip filters and tips |
US7151167B2 (en) | 2002-06-10 | 2006-12-19 | Phynexus, Inc. | Open channel solid phase extraction systems and methods |
JP4315366B2 (en) | 2003-02-03 | 2009-08-19 | 日東電工株式会社 | Chip filter and chip |
US6818264B1 (en) * | 2003-03-21 | 2004-11-16 | Joe Samperisi, Jr. | Corner/wall situated Christmas tree stand |
US20040224425A1 (en) * | 2003-05-08 | 2004-11-11 | Gjerde Douglas T. | Biomolecule open channel solid phase extraction systems and methods |
US7211289B2 (en) * | 2003-12-18 | 2007-05-01 | Endicott Interconnect Technologies, Inc. | Method of making multilayered printed circuit board with filled conductive holes |
US20050254995A1 (en) * | 2004-05-12 | 2005-11-17 | Harvard Apparatus, Inc. | Devices and methods to immobilize analytes of interest |
US20050281710A1 (en) | 2004-06-21 | 2005-12-22 | Crabtree James H | Low thermal mass multiple tube capillary sampling array |
-
2004
- 2004-09-30 EP EP04789532A patent/EP1677886A1/en not_active Withdrawn
- 2004-09-30 WO PCT/US2004/032958 patent/WO2005032688A1/en active Application Filing
- 2004-09-30 JP JP2006534299A patent/JP2007507721A/en active Pending
- 2004-09-30 US US10/955,377 patent/US7166212B2/en not_active Expired - Fee Related
-
2006
- 2006-12-05 US US11/633,713 patent/US7964097B2/en not_active Expired - Fee Related
-
2011
- 2011-05-11 US US13/105,833 patent/US20110210057A1/en not_active Abandoned
Patent Citations (98)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3570673A (en) * | 1968-09-07 | 1971-03-16 | Jenaer Glaswerk Schott & Gen | Separation column for liquid chromatography |
US4045352A (en) * | 1973-05-23 | 1977-08-30 | California Institute Of Technology | Ion-exchange hollow fibers |
US4043905A (en) * | 1974-08-26 | 1977-08-23 | Indiana University Foundation | Chromatographic separation columns with selectively modified active surfaces and methods for their preparations |
US4214020A (en) * | 1977-11-17 | 1980-07-22 | Monsanto Company | Processes for coating bundles of hollow fiber membranes |
US4293415A (en) * | 1979-04-27 | 1981-10-06 | Hewlett-Packard Company | Silica chromatographic column |
US4293413A (en) * | 1979-12-28 | 1981-10-06 | Baxter Travenol Laboratories, Inc. | Dialyzer blood circuit and bubble traps |
US4424127A (en) * | 1980-03-07 | 1984-01-03 | Johan Roeraade | Column for liquid and gas chromatography |
US4689267A (en) * | 1984-07-26 | 1987-08-25 | Shin-Etsu Chemical Co., Ltd. | Composite hollow fiber |
US4654265A (en) * | 1985-06-05 | 1987-03-31 | Ube Industries, Ltd. | Porous hollow fiber |
US4657742A (en) * | 1985-07-01 | 1987-04-14 | Ppg Industries, Inc. | Packed fiber glass reaction vessel |
US5154822A (en) * | 1986-07-28 | 1992-10-13 | 3I Research Exploitation Limited | Bonded chromatographic stationary phase |
US4999164A (en) * | 1986-10-20 | 1991-03-12 | Eppendorf-Netheler-Hinz Gmbh | Pipetting device comprising a retaining cone for holding a slip-on pipette tip and pipette tip for such pipetting device |
US4818264A (en) * | 1987-04-30 | 1989-04-04 | The Dow Chemical Company | Multicapillary gas chromatography column |
US5092219A (en) * | 1987-07-08 | 1992-03-03 | Thermedics Inc. | Selective decomposition of nitrite esters and nitramines |
US5092155A (en) * | 1987-07-08 | 1992-03-03 | Thermedics Inc. | High speed detection of vapors of specific compounds |
US4957620A (en) * | 1988-11-15 | 1990-09-18 | Hoechst Celanese Corporation | Liquid chromatography using microporous hollow fibers |
US5460781A (en) * | 1989-10-27 | 1995-10-24 | Fujirebio Kabushiki Kaisha | Hemoglobin sampler |
US5194333A (en) * | 1989-12-18 | 1993-03-16 | Tosoh Corporation | Packing material for reversed phase chromatography and process for its preparation |
US5160627A (en) * | 1990-10-17 | 1992-11-03 | Hoechst Celanese Corporation | Process for making microporous membranes having gel-filled pores, and separations methods using such membranes |
US5395521A (en) * | 1991-05-31 | 1995-03-07 | Board Of Regents, The University Of Texas System | Automated column equilibration, column loading, column washing and column elution |
US5876918A (en) * | 1993-03-08 | 1999-03-02 | Hydros, Inc. | Aligned fiber diagnostic chromatography with positive and negative controls |
US5616701A (en) * | 1993-09-27 | 1997-04-01 | Becton Dickinson And Company | DNA purification by solid phase extraction using a hydroxide-washed glass fiber membrane |
US5610290A (en) * | 1993-09-27 | 1997-03-11 | Becton Dickinson And Company | DNA purification by solid phase extraction using glass fiber membrane previously treated with trifluoroacetic acid, and then with fluoride ion, hydroxide ion, or Bcl3 |
US5438127A (en) * | 1993-09-27 | 1995-08-01 | Becton Dickinson And Company | DNA purification by solid phase extraction using a PCl3 modified glass fiber membrane |
US6638482B1 (en) * | 1993-11-01 | 2003-10-28 | Nanogen, Inc. | Reconfigurable detection and analysis apparatus and method |
US5429746A (en) * | 1994-02-22 | 1995-07-04 | Smith Kline Beecham Corporation | Antibody purification |
US5552047A (en) * | 1994-05-24 | 1996-09-03 | Terumo Kabushiki Kaisha | Hollow filament blood processing apparatus |
US6168948B1 (en) * | 1995-06-29 | 2001-01-02 | Affymetrix, Inc. | Miniaturized genetic analysis systems and methods |
US6117394A (en) * | 1996-04-10 | 2000-09-12 | Smith; James C. | Membrane filtered pipette tip |
US6306659B1 (en) * | 1996-06-28 | 2001-10-23 | Caliper Technologies Corp. | High throughput screening assay systems in microscale fluidic devices |
US5774779A (en) * | 1996-11-06 | 1998-06-30 | Materials And Electrochemical Research (Mer) Corporation | Multi-channel structures and processes for making such structures |
US6123905A (en) * | 1997-01-17 | 2000-09-26 | Matrix Technologies Corporation | Pipettor including an indicator and method of use |
US6048457A (en) * | 1997-02-26 | 2000-04-11 | Millipore Corporation | Cast membrane structures for sample preparation |
US6875354B1 (en) * | 1997-02-26 | 2005-04-05 | Millipore Corporation | Cast membrane structures for sample preparation |
US6635201B1 (en) * | 1997-02-26 | 2003-10-21 | Millipore Corporation | Cast membrane structures for sample preparation |
US6270674B1 (en) * | 1997-06-14 | 2001-08-07 | Akzo Nobel Nv | Membrane module with unilaterally embedded hollow fiber membranes |
US6794127B1 (en) * | 1997-06-16 | 2004-09-21 | Diversa Corporation | Capillary array-based sample screening |
US6174673B1 (en) * | 1997-06-16 | 2001-01-16 | Diversa Corporation | High throughput screening for novel enzymes |
US6866824B2 (en) * | 1997-06-16 | 2005-03-15 | Diversa Corporation | Capillary array-based sample screening |
US6045757A (en) * | 1997-06-30 | 2000-04-04 | Rainin Instrument Co., Inc. | Membrane filter pipette tip |
US6451260B1 (en) * | 1997-08-26 | 2002-09-17 | Dyax Corp. | Method for producing microporous elements, the microporous elements thus produced and uses thereof |
US20040171166A1 (en) * | 1998-01-12 | 2004-09-02 | Massachusetts Institute Of Technology | Method and apparatus for performing microassays |
US6387331B1 (en) * | 1998-01-12 | 2002-05-14 | Massachusetts Institute Of Technology | Method and apparatus for performing microassays |
US6743633B1 (en) * | 1998-01-12 | 2004-06-01 | Massachusetts Institute Of Technology | Method for performing microassays |
US6596237B1 (en) * | 1998-04-27 | 2003-07-22 | Nicholas F. Borrelli | Redrawn capillary imaging reservoir |
US6780582B1 (en) * | 1998-07-14 | 2004-08-24 | Zyomyx, Inc. | Arrays of protein-capture agents and methods of use thereof |
US6406921B1 (en) * | 1998-07-14 | 2002-06-18 | Zyomyx, Incorporated | Protein arrays for high-throughput screening |
US7247469B2 (en) * | 1998-07-14 | 2007-07-24 | Zyomyx, Inc. | Non-specific binding resistant protein arrays and methods for making the same |
US6576478B1 (en) * | 1998-07-14 | 2003-06-10 | Zyomyx, Inc. | Microdevices for high-throughput screening of biomolecules |
US6596545B1 (en) * | 1998-07-14 | 2003-07-22 | Zyomyx, Inc. | Microdevices for screening biomolecules |
US6582969B1 (en) * | 1998-07-14 | 2003-06-24 | Zyomyx, Inc. | Microdevices for high-throughput screening of biomolecules |
US6886824B2 (en) * | 1998-08-25 | 2005-05-03 | Minolta Co., Ltd. | Binding member removing apparatus, automatic document feeder, sheet processing apparatus, and image forming apparatus |
US6357484B1 (en) * | 1998-08-31 | 2002-03-19 | Uop Llc | Microporous structure defined by a multiplicity of singular channels and method of making |
US6231739B1 (en) * | 1998-09-11 | 2001-05-15 | The Perkin-Elmer Corporation | Multi-channel capillary electrophoresis device including sheath-flow cuvette and replacable capillary array |
US6387236B2 (en) * | 1998-09-11 | 2002-05-14 | Pe Corporation (Ny) | Multi-channel capillary electrophoresis device including sheath-flow cuvette and replaceable capillary array |
US6759126B1 (en) * | 1998-09-21 | 2004-07-06 | University Of South Florida | Solid phase microextraction fiber structure and method of making |
US6338802B1 (en) * | 1998-10-29 | 2002-01-15 | Pe Corporation (Ny) | Multi-well microfiltration apparatus |
US6309828B1 (en) * | 1998-11-18 | 2001-10-30 | Agilent Technologies, Inc. | Method and apparatus for fabricating replicate arrays of nucleic acid molecules |
US6174352B1 (en) * | 1998-11-24 | 2001-01-16 | Uop Llc | Round profile multi-capillary assembly and method of making |
US20040038316A1 (en) * | 1999-05-10 | 2004-02-26 | Robert Kaiser | Cell separation device and methods for use |
US20040147042A1 (en) * | 1999-05-28 | 2004-07-29 | Miklos Gratzl | Device for precise chemical delivery and solution preparation |
US7521020B2 (en) * | 1999-05-28 | 2009-04-21 | Case Western Reserve University | Device for precise chemical delivery and solution preparation |
US7118657B2 (en) * | 1999-06-22 | 2006-10-10 | President And Fellows Of Harvard College | Pulsed ion beam control of solid state features |
US6207049B1 (en) * | 1999-07-30 | 2001-03-27 | Agilent Technologies, Inc. | Multichannel capillary column |
US6992181B2 (en) * | 1999-10-28 | 2006-01-31 | Gyros Ab | DNA isolation method |
US6566145B2 (en) * | 2000-02-09 | 2003-05-20 | William E Brewer | Disposable pipette extraction |
US20030173284A1 (en) * | 2000-05-13 | 2003-09-18 | Baker Matthew John | Separation device |
US7276158B1 (en) * | 2000-06-09 | 2007-10-02 | Ashok K Shukla | Incision-based filtration/separation pipette tip |
US6537502B1 (en) * | 2000-07-25 | 2003-03-25 | Harvard Apparatus, Inc. | Surface coated housing for sample preparation |
US20050003211A1 (en) * | 2000-09-05 | 2005-01-06 | Hitachi, Ltd. | Removal method for coating of polymer coated glass capillary tubing and polymer coated glass capillary tubing |
US6780314B2 (en) * | 2000-11-01 | 2004-08-24 | Shinwa Chemical Industries, Ltd. | Separation column for chromatography, medium for solid phase extraction and sample injection system for chromatography |
US20020110495A1 (en) * | 2001-01-05 | 2002-08-15 | Denis Hunt | Devices and methods for purification |
US6416716B1 (en) * | 2001-04-20 | 2002-07-09 | Ashok Kumar Shukla | Sample preparation device with embedded separation media |
US20030068317A1 (en) * | 2001-04-20 | 2003-04-10 | William Lee | High capacity methods for separation, purification, concentration, immobilization and synthesis of compounds and applications based thereupon |
US20040191537A1 (en) * | 2001-06-13 | 2004-09-30 | Dieter Lubda | Restricted access material for spme |
US20030007897A1 (en) * | 2001-07-06 | 2003-01-09 | Andrew Creasey | Pipette tips |
US20070071649A1 (en) * | 2001-09-10 | 2007-03-29 | Marcus R Kenneth | Capillary-channeled polymer fibers as stationary phase media for spectroscopic analysis |
US6870165B2 (en) * | 2001-10-19 | 2005-03-22 | Biocal Technology, Inc. | Multi-color multiplexed analysis in a bio-separation system |
US7208072B2 (en) * | 2002-01-18 | 2007-04-24 | Biocal Technology, Inc. | Multi-segment cartridge for bio-separation with multiplexed fluorescence detection |
US7122640B2 (en) * | 2002-06-10 | 2006-10-17 | Phynexus, Inc. | Open channel solid phase extraction systems and methods |
US20060062701A1 (en) * | 2002-07-18 | 2006-03-23 | Hiroyuki Nakamura | Method of manufacturing microwave reaction device and microwave reaction device |
US7118671B2 (en) * | 2003-04-30 | 2006-10-10 | Institute For Roentgen Optics | Polycapillary chromatographic column and method of its manufacturing |
US20060216206A1 (en) * | 2003-05-29 | 2006-09-28 | Hudson William C | Solid phase extraction pipette |
US7595026B2 (en) * | 2003-05-29 | 2009-09-29 | Varian, Inc. | Solid phase extraction pipette |
US20050019951A1 (en) * | 2003-07-14 | 2005-01-27 | Gjerde Douglas T. | Method and device for extracting an analyte |
US20070017870A1 (en) * | 2003-09-30 | 2007-01-25 | Belov Yuri P | Multicapillary device for sample preparation |
US7166212B2 (en) * | 2003-09-30 | 2007-01-23 | Chromba, Inc. | Multicapillary column for chromatography and sample preparation |
US20070075007A1 (en) * | 2003-09-30 | 2007-04-05 | Belov Yuri P | Multicapillary column for chromatography and sample preparation |
US20050139536A1 (en) * | 2003-09-30 | 2005-06-30 | Belov Yuri P. | Multicapillary column for chromatography and sample preparation |
US7964097B2 (en) * | 2003-09-30 | 2011-06-21 | Belov Yuri P | Multicapillary column for chromatography and sample preparation |
US20070111194A1 (en) * | 2003-12-15 | 2007-05-17 | Preentec Ag | Method for the concentration and purification of biological compounds |
US20050178709A1 (en) * | 2004-01-23 | 2005-08-18 | Ngk Insulators, Ltd. | Supports for solid phase extraction |
US7271895B2 (en) * | 2004-04-09 | 2007-09-18 | Institute For Roentgen Optics | Fluorescent sensor on basis of multichannel structures |
US20060201881A1 (en) * | 2004-08-10 | 2006-09-14 | Clemson University | Capillary-channeled polymeric fiber as solid phase extraction media |
US20060093518A1 (en) * | 2004-10-29 | 2006-05-04 | Shukla Ashok K | Device containing non-covalently bound biomolecules on solid support |
US20060118491A1 (en) * | 2004-12-03 | 2006-06-08 | Gjerde Douglas T | Method and device for desalting an analyte |
US20070116607A1 (en) * | 2005-11-23 | 2007-05-24 | Pharmacom Microlelectronics, Inc. | Microsystems that integrate three-dimensional microarray and multi-layer microfluidics for combinatorial detection of bioagent at single molecule level |
US20070215543A1 (en) * | 2006-03-14 | 2007-09-20 | Mettler-Toledo Autochem, Inc. | Small volume liquid-liquid extraction device and method of use |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8980093B2 (en) | 2003-09-30 | 2015-03-17 | Yuri P. Belov | Multicapillary device for sample preparation |
WO2019042989A1 (en) * | 2017-08-29 | 2019-03-07 | Labomatic Instruments Ag | Tube assembly |
Also Published As
Publication number | Publication date |
---|---|
WO2005032688A1 (en) | 2005-04-14 |
JP2007507721A (en) | 2007-03-29 |
US7166212B2 (en) | 2007-01-23 |
EP1677886A1 (en) | 2006-07-12 |
US20070075007A1 (en) | 2007-04-05 |
US20050139536A1 (en) | 2005-06-30 |
US7964097B2 (en) | 2011-06-21 |
WO2005032688A9 (en) | 2005-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7964097B2 (en) | Multicapillary column for chromatography and sample preparation | |
US5583281A (en) | Microminiature gas chromatograph | |
Robson et al. | Capillary electrochromatography: A review | |
Tsuda et al. | Studies of open-tubular micro-capillary liquid chromatography: II. Chemically bonded octadecylsilane stationary phase | |
Yu et al. | Towards stationary phases for chromatography on a microchip: Molded porous polymer monoliths prepared in capillaries by photoinitiated in situ polymerization as separation media for electrochromatography | |
Zotou | An overview of recent advances in HPLC instrumentation | |
EP1576365A1 (en) | Microminiature gas chromatograph column | |
US20110042566A1 (en) | Conductive conduits for chemical analyses, and methods for making such conduits | |
EP2561345A2 (en) | Method of packing chromatographic columns | |
Tsuda et al. | Open-tubular microcapillary liquid chromatography with 20-μm ID columns | |
Jakubetz et al. | On the feasibility of miniaturized enantiomeric separation by liquid chromatography (OTLC) and open tubular electrochromatography (OTEC) | |
US6267884B1 (en) | Capillary columns employing monodispersed particles | |
US6821418B2 (en) | Surface modification of a porous polymer monolith and products therefrom | |
JP2010527003A (en) | Chromatographic and electrophoretic separation media and equipment | |
JP2010504521A (en) | Multi-capillary device for sample preparation | |
Tomáš et al. | Multidimensional liquid phase separations for mass spectrometry | |
Novotny | Recent developments in analytical chromatography | |
Pruim et al. | Microfluidic pressure driven liquid chromatography of biologically relevant samples | |
WO2008145457A1 (en) | Improved capillary column for gas chromatography | |
Novotny | Microcolumn liquid chromatography: a tool of potential significance in biomedical research. | |
Nogueira | Stir bar sorptive extraction | |
Lindner et al. | Trends in enantioselective high performance liquid chromatography | |
US7938961B2 (en) | Capillary loop with a built-in retaining frit | |
US20180111060A1 (en) | Gas liquid separator for chromatography applications | |
JP2023167508A (en) | Packing material-containing microcolumn |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |