WO1996023572A1 - Gradient density filter - Google Patents
Gradient density filter Download PDFInfo
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- WO1996023572A1 WO1996023572A1 PCT/US1995/016545 US9516545W WO9623572A1 WO 1996023572 A1 WO1996023572 A1 WO 1996023572A1 US 9516545 W US9516545 W US 9516545W WO 9623572 A1 WO9623572 A1 WO 9623572A1
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- WIPO (PCT)
- Prior art keywords
- filter
- sheets
- microfibers
- polypropylene
- disk
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Classifications
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
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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
- B01J20/28—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
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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
- B01J20/28—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
- B01J20/28023—Fibres or filaments
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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
- B01J20/28—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
- B01J20/28028—Particles immobilised within fibres or filaments
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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
- B01J20/28—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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- B01J20/28—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
- B01J20/28052—Several layers of identical or different sorbents stacked in a housing, e.g. in a column
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0622—Melt-blown
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0627—Spun-bonded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/065—More than one layer present in the filtering material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/065—More than one layer present in the filtering material
- B01D2239/0654—Support layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1233—Fibre diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1291—Other parameters
Definitions
- This invention relates to a filter comprising nonwoven, blown polypropylene microfiber sheets which is especially useful in solid phase extraction processes.
- the effective pore size of the filter decreases with increasing depth.
- Depth filters for blood filtration are described in U.S. Patent No. 4,701,267, where multiple layers of nonwoven mats of increasing bulk density are used as filters. These mats can be made from synthetic fibers, semi-synthetic fibers, regenerated fibers, inorganic fibers and natural fibers, with polyester being exemplified.
- the nonwoven mats comprise fibers of an average diameter of from 0.3 to less than 3 ⁇ m.
- U.S. Patent No. 3,353,682 describes a multilayer depth filter for biological filtrations, where the filter is made in a wet-laid fashion from short fibers.
- a typical construction includes a fine filter having pores in the range of 10 to 25 ⁇ m and a course filter having pores in the range of 70 to 150 ⁇ m. These filters are said to be capable of absolutely removing from fluids particles "as small as 25 microns in size, and even particles of 10 microns down to 0.03 microns and smaller.” Above the fine filtering portion of the filter is a layer that protects the fine filter from being clogged by particles up to 150 ⁇ m in size. Thus, the overall construction acts as a type of depth filter. In addition to natural fibers, synthetic fibers including polypropylene are said to be useful. Binders for the fibers are discussed in detail.
- U.S. Patent No. 4,925,572 describes a leukocyte filter for blood which uses gradient density filters made from nonwoven materials.
- One embodiment describes a series of 15, 10, and 7 ⁇ m polybutyleneterephthalate (PBET) filters below a "gel filter” made from 30 to 50 ⁇ m PBET. Modification of the fiber surface, by grafting, priming, or other "preconditioning means” is required to decrease the critical wetting surface tension of the filter mats.
- U.S. Patent 5,338,448 describes solid phase chromatographic column which employs a "guard disk” as a protective pad above the absorptive material of the column, retaining both particlesand dissolved contaminants.
- the guard disk comprises sorptive chromatographic material incorporated into a woven or nonwoven fabric or membrane, or may comprise a fabric or membrane matrix having stationary phase functional groups covalently bonded to the fabric or membrane structure itself.
- the guard disk must contain sorptive material.
- the protective disk may comprise a plurality of fabric or membrane layers, and pore sizes for the protective disks are in the range of 0.1 to 5 ⁇ m.
- the present invention provides a filter comprising a plurality of sheets of blown polypropylene microfibers, at least one of those sheets having an effective pore diameter smaller than the effective pore diameter of at least one sheet upstream therefrom, all of the polypropylene fibers having a critical wetting surface tension less than about 50 dynes/cm, the aggregate average effective diameter of the microfibers being at least 3 ⁇ m.
- the CWST can be determined by applying to the surface of a porous medium a series of liquids having surface tensions that vary by a set amount (e.g., 2 to 4 dynes/cm) and observing the absorption or non-absorption of each liquid.
- a set amount e.g. 2 to 4 dynes/cm
- the polypropylene microfibers used in the sheets of the filters of the present invention preferably are "virgin".
- they are essentially free of binders, finishing agents, and other adjuvants which often are added to or coated on polypropylene fibers during or after the formation of a microfibrous web.
- Such fibers will, however, contain those materials that are added during the polypropylene formation process (e.g., antioxidant).
- "Virgin" polypropylene microfibers contain no additives other than those inherent in the synthesis of the polypropylene.
- the filter of the present invention is especially useful where the fluid to be filtered is a biological fluid, such as blood, plasma, serum, urine, or some other such fluid.
- biological fluids often contain small amounts of insoluble materials that can interfere with analyses to be performed on those fluids. Removal of such insoluble materials is a continuing concern to those who perform medical and chemical analyses, because such fluids must be "clean" (i.e., free of insoluble materials) to be analyzed accurately.
- solid phase extraction is meant the removal or isolation of one or more soluble analytes from a fluid by means of sorption to immobilized solid particles.
- Such solid phase extractions normally are performed using packed beds of particles that are capable of sorbing the analyte(s). More recently, however, solid phase extractions have been performed using disks in which the particles are entrapped in porous fibrous polymeric or glass fiber webs.
- the filter of the present invention has a very small dead volume (e.g., about 40 ⁇ L). Therefore, the filter of the present invention has little negative effect on the required elution volume.
- FIG. 1 is a greatly enlarged perspective view showing one embodiment of a gradient density polypropylene filter of the present invention.
- FIG. 2 is a greatly enlarged exploded view of the multilayer polypropylene gradient density filter from FIG. 1.
- FIG. 3 is a greatly enlarged perspective view of a solid phase extraction disk cartridge in which one embodiment of the multilayer polypropylene gradient density filter of the present invention has been placed above the solid phase extraction disk or the cartridge.
- FIG. 4 is a greatly enlarged exploded view of the solid phase extraction disk cartridge of FIG. 3.
- filter 10 comprises a plurality of sheets of blown polypropylene microfibers 12.
- at least one of downstream sheets 14 or 16 must have an e fective pore diameter that is smaller than the effective pore diameter of at least one sheet upstream therefrom, 16 or 18 respectively.
- This gradient density characteristic provides improved performance over filters having a uniform pore diameter.
- filter 10 comprises at least three sheets (14, 16, and 18), each of which has an effective pore diameter different from those of the other two sheets.
- the effective pore diameter of a given sheet is a function of, inter alia, the effective diameter of the fibers that make up that sheet.
- Sheets 14, 16, and 18 are preferably arranged (from upstream to downstream) in order of decreasing effective pore diameters, in other words, decreasing fiber diameter. If desired, a multiplicity of any of sheets 14, 16, or 18 can be used. Sheets of various fiber diameters 12 are then laminated to form an essentially unitary construction, i.e., filter 10. Lamination can be accomplished by any of a number of well known means in the art including nip rolling, hand pressing, etc. Cover layer 20 can be added to plurality of sheets 12 of filter 10. Cover layer 20 is preferably more rigid than any of sheets 12. Cover layer 20 helps to maintain the overall integrity of filter 10 (or of a solid phase extraction system in which filter 10 is incorporated) during transportation, handling, and/or use.
- cover layer 20 is made of a polymeric material so that filter 10 (or a solid phase extraction system in which filter 10 is incorporated) maintains a high degree of chemical inertness.
- cover layer 20 will be made of the same polymer (i.e., polypropylene) as sheets 12.
- Cover layer 20 can take various forms, including but not limited to, a screen, a scrim, or a membrane. Preferably, the form chosen will allow cover layer 20 to be laminated along with sheets 12.
- a preferred cover layer 20 is a spunbonded polypropylene membrane, such as a TyparTM membrane (Reemay Inc.; Old Hickory, TN), which is known by the trade name TektonTM outside of the Western hemisphere.
- TyparTM 3801 sheets have been found to be especially useful because of their high rigidity. Additionally, where a membrane is used as cover layer 20, it can provide additional filtering capability (i.e., for a relatively coarse material in the liquid to be filtered).
- a membrane is used as cover layer 20, it can provide additional filtering capability (i.e., for a relatively coarse material in the liquid to be filtered).
- FIGs. 1 and 2 an embodiment of the filter of the present invention that includes one sheet 18 of polypropylene microfibers with, for example, effective diameter of about 15 ⁇ m, one sheet 16 of polypropylene microfibers with, for example, an effective fiber diameter of about 7 ⁇ m, and five sheets 14 of polypropylene microfibers with, for example, an effective diameter of about 3 ⁇ m, is shown.
- sheets 12 are possible and within the scope of the present invention.
- sheet 16 (where the effective diameter of the polypropylene microfibers is about 7 ⁇ m) can be removed without deleteriously effecting the performance of filter 10.
- an arrangement of, for example, sheets with effective diameters of 13, 8, and 4 ⁇ m (or some other such combination) can be effective.
- Blown microfiber sheets 12 can be prepared according to processes well known in the art. See, e.g., V. A. Wente, "Superfine Thermoplastic Fibers,” Industrial and Engineering Chemistry, vol. 48, no. 8, 1342-46 (Aug. 1956) and V.A. Wente et al., "Manufacture of Superfine Organic Fibers," Navy Research Laboratory Report 4364 (May 25, 1954).
- Polypropylene resin useful in making microfibers for sheets 12 is available from a variety of sources, including Exxon Chemical Co. (Houston, TX), as Grade PP3505G.
- the addition of binders, finishing agents, or other adjuvants commonly used during the fiber formation process preferably is scrupulously avoided.
- any contaminant that might potentially leach from filter 10 during use can interfere with analysis being performed on the filtered liquid (i.e., eluent). Accordingly, the addition of any such leachable material is preferably avoided.
- the microfibers of sheets 12 have a CWST less than about 50, preferably less than about 45, and more preferably less than about 40. Most preferably, the microfibers of sheets 12 have a CWST equal to, or very nearly equal to, that of untreated polypropylene (i.e., about 25 dynes/cm).
- Webs i.e., sheets prepared from such microfibers are effective in removing insoluble materials from fluids that might contain analytes on the basis of their size, dimension, and/or affinity. Most analytes do not have an affinity for untreated polypropylene and thus pass through the pores between the microfibers.
- sheets 12 having the effective fiber diameters necessary to provide filter 10 with the desired gradiation, optionally along with cover layer 20 in the form of a membrane, screen, scrim, etc., are layered in a stacked construction and drawn over a series of drums at a rate of from about 8 to about 80 m/min.
- This laminated stacked construction is then slit into strips from which filter 10 of a desired size and shape is cut by means of, for example, a die.
- the aggregate average effective diameter of the microfibers of sheets 12 is at least about 3 ⁇ m, preferably at least about 3.25 ⁇ m, more preferably at least about 3.5 ⁇ m, and most preferably at least about 4 ⁇ m. (To calculate aggregate average effective fiber diameter, one sums the effective fiber diameter of each of the individual sheets then divides by the total number of sheets.) Despite the fact that the aggregate average effective fiber diameter of sheets 12 is greater than at least about 3 ⁇ m, it has been found not to compromise the ability of filter 10 to remove insoluble materials from fluids, particularly biological fluids. An advantage of the filter of the present invention is that its thickness is less than that of most commonly used gradient density filters.
- a representative example of the filter of the present invention is about 2.5 mm thick (with at least 90% of the volume thereof being air). This small thickness helps to decrease the amount of inherent dead volume in the filter. Thus, when a filter of the present invention is used in combination with an extraction medium, the filter of the present invention has little negative effect on the required elution volume.
- the filter of the present invention is especially useful where the fluid to be filtered is a biological fluid. These fluids often contain small amounts of insoluble materials that can interfere with analyses to be performed on those fluids.
- the filter of the present invention has been found to be about as effective as glass fiber gradient density filters in removing such insoluble materials. Additionally, the filter of the present invention has a very small dead volume, which helps to increase the accuracy of quantitative analyses performed on fluids filtered therethrough.
- solid phase extraction disk cartridge 30 includes inlet opening 32 and outlet opening 34, between which is located sample reservoir 36.
- Cartridge 30 can be made of a variety of materials including polypropylene, polyethylene, glass, nylon, or any commonly used material that is processable into shapes, chemically inert, resistant to common laboratory solvents, and resistant to acidic and basic conditions. Polypropylene is a preferred material.
- base 38 At the bottom of sample reservoir 36 is located base 38.
- Base 38 supports solid phase extraction disk 40.
- a nonwoven sheet (not shown), made from the same type of material as that used to make cartridge 30, can be placed between base 38 and disk 40 to provide support for disk 40 and to allow for even flow distribution across the surface of disk 40.
- a preferred type of nonwoven sheet is a VeratecTM 141583 polypropylene sheet (Veratec Co.; Walpole, MA).
- a preferred type of extraction disk 40 is a fibrous polymeric membrane in which is entrapped sorptive particles, although glass fiber membranes in which sorptive particles are entrapped can also be useful.
- sorptive particles are silica, derivatized silica, bonded silica, activated carbon, derivatized and underivatized poly(styrene divinylbenzene), and alumina.
- useful so tive particles are those described in U.S. Patent No. 5,279,742.
- useful paniculate material is said to include those particles that are substantially insoluble in aqueous liquid and organic liquid such as water and ethyl acetate. Not more than 1.0 g of paniculate will dissolve in 100 g of aqueous or organic liquid into which paniculate is mixed at 20°C.
- the paniculate material can be at least one of an organic polymer such as polydivinylbenzene, or a copolymer, preferably a copolymer of styrene and divinylbenzene (75-25 to 99.00-0.01), or poly(meth)acrylic acid esters, and derivatives thereof, particularly those containing ion-exchanged groups such as sulfonated or aminated groups.
- an organic polymer such as polydivinylbenzene, or a copolymer, preferably a copolymer of styrene and divinylbenzene (75-25 to 99.00-0.01)
- poly(meth)acrylic acid esters and derivatives thereof, particularly those containing ion-exchanged groups such as sulfonated or aminated groups.
- Suitable sorptive particles that optionally can be used include any panicle that can be coated with aqueous- or organic-insoluble, non-swellable sorbent material or the surface (external and/or internal) of which can be derivatized to provide a coating of insoluble, non-swellable sorbent material.
- Such panicles include inorganic oxides such as silica, alumina, titania, zirconia, and other ceramics to which are covalently bonded organic groups.
- Preferred inorganic oxide paniculate materials are silica and zirconia because they are commercially available, with silica being particularly preferred because of the ease in bonding a variety of hydrophobic and hydrophilic ligands and coatings onto its surface.
- the insoluble, aqueous non-swellable sorbent coatings generally have a thickness in the range of one molecular monolayer to about 100 nm.
- Such particles having coated surfaces are well known in the an. See, for example, Snyder and Kirkland, "Introduction to Modern Liquid Chromatography", 2d ed., John Wiley & Sons, Inc. (1979) and H. Figge et al., "Journal of Chromatography", 351, 339-408 (1986).
- modified silica paniculate silica particles having covalently bonded thereto organic groups, preferably cyanopropyl, cyclohexyl, phenyl, C 2 (ethyl), C 4 (butyl), C 8 (octyl), and Cig (octadecyl) groups.
- Coatings that can be applied to inorganic paniculate can be either thin mechanical coatings of insoluble, non-swellable polymers such as crosslinked silicones, polybutadienes, etc., or covalently bonded organic groups such as aliphatic groups of varying chain length (e.g., C 2 , C 4 , C$, and Cig) and organic groups including aliphatic and aromatic groups.
- Preferred groups include amino, cyano, hydroxyl, phenyl, cyclohexyl, and other groups that alter the polarity of the coating.
- the support particle in this case acts primarily as a carrier for the organic coatings. Many such coated particles are commercially available.
- Cig bonded phase silica is available from Alltech (Deerfield, H.) or Varian Sample Preparation Products (Harbor City, CA). Variation in chemical composition of the coatings can provide selectivity in molecular separations and polarity.
- retaining ring 42 can be located directly on extraction disk 40.
- Retaining ring 42 can be made of any material that is processable into shapes, chemically inert, stable at a variety of pHs, and resistant to common laboratory solvents.
- gradient density polypropylene microfibrous filter 44 can have any of the constructions described previously.
- Filter 44 can have any of the constructions described previously.
- a second retaining ring (not shown). This second retaining ring is of the same general construction as retaining ring 42 and can be made from the same or a different material.
- Liquid that has passed through membrane 40 exits cartridge 30 through tip 46 that surrounds outlet opening 34.
- a receiving vessel (not shown) can be located beneath cartridge 30 to catch the filtered liquid exiting therefrom.
- the gradient density filter of the present invention can also be useful when used with a column packed with sorptive particles.
- the sorptive particles need not be entrapped in extraction disk 40 for the filter of the present invention to screen out insoluble materials that can interfere with the extraction being performed on liquid that is passing by the sorptive particles.
- the filter and disk were washed with a 75:25 (v/v) water-acetonitrile (ACN) solution and air dried under the same vacuum for 5 seconds.
- the drugs were eluted from the disk with two aliquots of 0.2 mL of a 68: 15: 17 (v/v/v) mixture of ACN-Buffer A-methanol.
- Percent recovery ofeach drug was measured by liquid chromatography, using a Waters Instruments Model 486 HPLC (Waters Corp.; Milford, MA) fitted with a 15 cm x 4.6 mm inner diameter cyanopropyl column (Supelco Inc.; Bellefonte, PA), using a mobile phase of 60:25:15 (v/v/v) ACN-Buffer A-methanol at 2.0 mlJmin and a column temperature of 30°C. The presence and amount ofeach drug were detected by UV absorbance at 215 nm with a detector sensitivity of 0.005 AUFS. Percent recovery was measured relative to an equal amount ofeach analyte directly injected into the instrument.
- Nylon filter with an effective pore size of 0.45 ⁇ m (Chrom Tech, Inc.; Apple Valley, MN)
- Nylon filter with an effective pore size of 0.2 ⁇ m (Chrom Tech)
- 3M Liquid Disk Filters provide flow rates equal to or faster than glass fiber filters.
- Example 3 Comparison of Drug Recovery from EmporeTM Extraction Disks with Blown Polypropylene Microfiber vs. Glass Microfiber Filters
- C-8 EmporeTM 7mm/3mL solid phase extraction disk cartridges (3M) were fitted with filters above the disks.
- the filters were: (1) a construction of 8 sheets of nonwoven blown polypropylene microfibers, 10 ⁇ m effective diameter, atop 5 sheets of nonwoven blown polypropylene microfibers, 3.4 ⁇ m effective diameter (3M Filtration Products; St. Paul, MN); (2) a gradient density glass microfiber filter designated "GD1M' (Whatman, Inc.); and (3) a gradient density glass microfiber filter designated "GF/D VA" (Whatman, Inc.).
- Example 6 Human Plasma Flow Rates with and without Graded Density Filter
- a three layer gradient density filter was constructed from blown polypropylene microfiber sheets, described in Example 4, as follows: one sheet having fibers with an effective diameter of 15 ⁇ m was placed on one sheet having fibers with an effective diameter of 7 ⁇ m which was placed on five sheets having fibers with an effective diameter of 3.4 ⁇ m (hereafter referred to as the "1/1/5 filter").
- a circular section was cut from the 1/1/5 filter and placed in a 7 mm/3 mL C-18 EmporeTM solid phase extraction disk cartridge.
- Flow times for 1.0 mL of human plasma diluted with 0.5 mL Buffer A through the extraction disk, with and without a filter, at 38.1 cm Hg vacuum were measured with fresh plasma and with plasma that had been refrigerated for three days.
- the refrigerated sample was quite viscous, containing more fibrin and microbial content than the fresh sample. The results are shown below in Table 6.
- Example 7 Effect of Cover Layer
- cover layers which aid in holding the 1/1/5 filter (see Example 6) in place during extraction and elution, were compared: (1) a polypropylene screen (Internet Co.; New Hope, MN); (2) a TyparTM 3801 spunbonded polypropylene membrane; and (3) the molded polypropylene ring commercially supplied with an EmporeTM 7 mm/3mL solid phase extraction disk cartridge.
- the 1/1/5 filter was also used with a SPECTM»3ML solid phase extraction device containing a glass fiber disk in which is entrapped 15 mg C-18 bonded silica microparticles (Ansys Co.; Irvine, CA).
- EmporeTM cartridge with filter, polypropylene screen as cover layer 3.
- EmporeTM cartridge with filter, molded polypropylene ring as cover layer is shown in FIG. 5 .
- EmporeTM cartridge with filter, spundbonded polypropylene membrane as cover layer 6) EmporeTM cartridge with filter, spundbonded polypropylene membrane as cover layer. 7) Approximately 1 mL of plasma-buffer solution remained in cartridge after 15 minutes.
- a stock solution that contained 10.0 ⁇ g of both diazepam and nordiazepam (both available from Sigma Chemicals) per mL DI water was prepared. Samples of 1.0 mL human plasma or 1.0 mL DI water were diluted with 0.5 mL 0.05 M pH 5.0 ammonium acetate buffer ("Buffer C") and doped with 50 ⁇ L of the stock solution, such that the total volume ofeach sample was 1.55 mL.
- Buffer C pH 5.0 ammonium acetate buffer
- the samples were passed, under 38.1 cm Hg vacuum, through a C-18 EmporeTM 7 mm 3 mL solid phase extraction disk cartridge containing either (1) a 1/1/5 filter (see Example 6), referred to in Table 8 as "Filter B", with a cover layer of TyparTM 3801 spunbonded polypropylene web, a polypropylene screen, or a standard EmporeTM polypropylene ring; or (2) a filter containing eight sheets of blown polypropylene microfibers having an effective fiber diameter of 10 ⁇ m over five sheets of blown polypropylene microfibers having an effective fiber diameter of 3.4 ⁇ m, referred to in Table 8 as "Filter A”.
- the extraction disks were washed with 0.5 mL 25:75 ACN- water solution and eluted twice with 0.2 mL methanol, and the eluate was stirred with an additional 0.4 mL Buffer C.
- the amount ofeach drug in the eluate was measured by liquid chromatography, using a Waters Instruments Model 486 HPLC fitted with a 15 cm x 4.6 mm SupelcoTM LC-18DB column and a SupelcoTM C-18 guard column at a column temperature of 30° C.
- the mobile phase a 55:45 (v/v) ACN-Buffer C solution, was pumped at 2.0 mlJmin.
- the drugs were detected by UV absorbance at 242 nm with a sensitivity of 0.005 AUFS. Results are shown below in Table 8.
- Dead volumes of cartridges that include filters held in place by polypropylene screens and by TyparTM spunbonded polypropylene webs were determined and compared to dead volumes of cartridges without filters.
- EmporeTM 7mm/3mL solid phase extraction disk cartridges were prepared without a filter, with a 1/1/5 filter having a polypropylene screen cover layer, and with a 1/1/5 filter having a TyparTM membrane cover layer.
- each cartridge was weighed dry, each was conditioned by pulling 0.25 mL methanol followed by 0.5 mL DI water through the disk under 38.1 cm Hg vacuum, with the vacuum being left on for two seconds of drying. Each cartridge was then weighed again. Thereafter, the cartridges were treated with two rinses of 0.2 mL of a mobile phase of a 68:17:15 (v/v/v) mixture of acetonitrile-methanol-Buffer A, with the vacuum being left on for two seconds of drying, then weighed. Holdup volumes of water and mobile phase are reported in Table 9.
- the mean flow time for cartridges fitted with the screen cover layer was 228 seconds (range: 165 to 305 seconds), whereas the mean flow time for cartridges fitted with a TyparTM web cover layer was 158 seconds (range: 140 to 192 seconds). These flow times show that the TyparTM web cover layer generally provides faster flow times and improved efficiency by adding an additional layer that has filtration capability.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nanotechnology (AREA)
- Filtering Materials (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU45240/96A AU4524096A (en) | 1995-02-01 | 1995-12-19 | Gradient density filter |
EP95943886A EP0806979B1 (en) | 1995-02-01 | 1995-12-19 | Gradient density filter |
BR9510447A BR9510447A (en) | 1995-02-01 | 1995-12-19 | Filter for removing insoluble materials from a liquid and solid phase extraction device |
DE69512088T DE69512088T2 (en) | 1995-02-01 | 1995-12-19 | FILTER WITH DENSITY GRADIENT |
JP52352496A JP3670288B2 (en) | 1995-02-01 | 1995-12-19 | Density gradient filter |
MXPA/A/1997/005645A MXPA97005645A (en) | 1995-02-01 | 1997-07-25 | Gradie density filter |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/382,281 US5472600A (en) | 1995-02-01 | 1995-02-01 | Gradient density filter |
US08/382,281 | 1995-02-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996023572A1 true WO1996023572A1 (en) | 1996-08-08 |
Family
ID=23508278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/016545 WO1996023572A1 (en) | 1995-02-01 | 1995-12-19 | Gradient density filter |
Country Status (8)
Country | Link |
---|---|
US (1) | US5472600A (en) |
EP (1) | EP0806979B1 (en) |
JP (1) | JP3670288B2 (en) |
KR (1) | KR100426526B1 (en) |
AU (1) | AU4524096A (en) |
BR (1) | BR9510447A (en) |
DE (1) | DE69512088T2 (en) |
WO (1) | WO1996023572A1 (en) |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0370584A1 (en) * | 1988-11-23 | 1990-05-30 | Akzo N.V. | Filter and process for preparing a leucocyte-poor platelet suspension |
EP0391726A2 (en) * | 1989-04-07 | 1990-10-10 | JOHNSON & JOHNSON MEDICAL, INC. | Improved filtration medium and face mask containing the same |
WO1993011218A1 (en) * | 1991-12-02 | 1993-06-10 | Qiagen Gmbh | Method and device for the isolation of cell components, such as nucleic acids, from natural sources |
EP0555706A1 (en) * | 1992-01-29 | 1993-08-18 | Shimadzu Corporation | Agitation stabilizer in solidphase peptide synthesizer |
WO1993017774A1 (en) * | 1992-03-05 | 1993-09-16 | Pall Corporation | Filter and method for obtaining platelets |
WO1995024418A1 (en) * | 1994-03-10 | 1995-09-14 | Minnesota Mining And Manufacturing Company | Method of isolating and purifying a biomacromolecule |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US956832A (en) * | 1909-01-12 | 1910-05-03 | Theobald Friedrich Seitz | Filter. |
US3353682A (en) * | 1966-02-28 | 1967-11-21 | Pall Corp | Fluid-permeable fibrous multilayer materials and process of making the same |
US3847821A (en) * | 1973-10-19 | 1974-11-12 | Minnesota Mining & Mfg | Separator for removing a dispersed liquid phase from a continuous liquid phase |
US4483771A (en) * | 1983-08-08 | 1984-11-20 | Elizabeth Koch | Multi-layer filter |
EP0155003B1 (en) * | 1984-03-15 | 1990-07-04 | ASAHI MEDICAL Co., Ltd. | Filtering unit for removing leukocytes |
US4925572A (en) * | 1987-10-20 | 1990-05-15 | Pall Corporation | Device and method for depletion of the leukocyte content of blood and blood components |
JPH01180213A (en) * | 1988-01-08 | 1989-07-18 | Toray Ind Inc | Filter element |
CA2059398C (en) * | 1991-02-07 | 1999-05-25 | Craig G. Markell | Solid phase extraction medium |
US5338448A (en) * | 1992-10-16 | 1994-08-16 | Sarasep, Inc. | Method of preventing contamination of a chromatography column |
-
1995
- 1995-02-01 US US08/382,281 patent/US5472600A/en not_active Expired - Lifetime
- 1995-12-19 JP JP52352496A patent/JP3670288B2/en not_active Expired - Fee Related
- 1995-12-19 WO PCT/US1995/016545 patent/WO1996023572A1/en active IP Right Grant
- 1995-12-19 AU AU45240/96A patent/AU4524096A/en not_active Abandoned
- 1995-12-19 DE DE69512088T patent/DE69512088T2/en not_active Expired - Fee Related
- 1995-12-19 EP EP95943886A patent/EP0806979B1/en not_active Expired - Lifetime
- 1995-12-19 BR BR9510447A patent/BR9510447A/en not_active IP Right Cessation
- 1995-12-19 KR KR1019970705231A patent/KR100426526B1/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0370584A1 (en) * | 1988-11-23 | 1990-05-30 | Akzo N.V. | Filter and process for preparing a leucocyte-poor platelet suspension |
EP0391726A2 (en) * | 1989-04-07 | 1990-10-10 | JOHNSON & JOHNSON MEDICAL, INC. | Improved filtration medium and face mask containing the same |
WO1993011218A1 (en) * | 1991-12-02 | 1993-06-10 | Qiagen Gmbh | Method and device for the isolation of cell components, such as nucleic acids, from natural sources |
EP0555706A1 (en) * | 1992-01-29 | 1993-08-18 | Shimadzu Corporation | Agitation stabilizer in solidphase peptide synthesizer |
WO1993017774A1 (en) * | 1992-03-05 | 1993-09-16 | Pall Corporation | Filter and method for obtaining platelets |
WO1995024418A1 (en) * | 1994-03-10 | 1995-09-14 | Minnesota Mining And Manufacturing Company | Method of isolating and purifying a biomacromolecule |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT502437B1 (en) * | 2005-10-17 | 2007-09-15 | Andritz Ag Maschf | FILTER ELEMENT |
US11439933B2 (en) | 2013-08-30 | 2022-09-13 | Emd Millipore Corporation | High capacity composite depth filter media with low extractables |
US11660555B2 (en) | 2013-08-30 | 2023-05-30 | Emd Millipore Corporation | High capacity composite depth filter media with low extractables |
US11772020B2 (en) | 2013-08-30 | 2023-10-03 | Emd Millipore Corporation | High capacity composite depth filter media with low extractables |
Also Published As
Publication number | Publication date |
---|---|
EP0806979A1 (en) | 1997-11-19 |
DE69512088D1 (en) | 1999-10-14 |
AU4524096A (en) | 1996-08-21 |
BR9510447A (en) | 1998-05-19 |
KR100426526B1 (en) | 2004-07-23 |
US5472600A (en) | 1995-12-05 |
MX9705645A (en) | 1997-10-31 |
DE69512088T2 (en) | 2000-05-25 |
KR19980701834A (en) | 1998-06-25 |
JP3670288B2 (en) | 2005-07-13 |
JPH10513113A (en) | 1998-12-15 |
EP0806979B1 (en) | 1999-09-08 |
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