CA1317714C - Polyaldehyde activated membranes - Google Patents
Polyaldehyde activated membranesInfo
- Publication number
- CA1317714C CA1317714C CA000576838A CA576838A CA1317714C CA 1317714 C CA1317714 C CA 1317714C CA 000576838 A CA000576838 A CA 000576838A CA 576838 A CA576838 A CA 576838A CA 1317714 C CA1317714 C CA 1317714C
- Authority
- CA
- Canada
- Prior art keywords
- membrane
- polyaldehyde
- mixture
- recited
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 171
- 229920001744 Polyaldehyde Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 54
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012982 microporous membrane Substances 0.000 claims abstract description 40
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 34
- 150000001299 aldehydes Chemical group 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 31
- 230000027455 binding Effects 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000005266 casting Methods 0.000 claims description 18
- 230000003213 activating effect Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- -1 polyacrolein Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 229920000936 Agarose Polymers 0.000 claims description 3
- GRFFKYTUNTWAGG-UHFFFAOYSA-N chloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N GRFFKYTUNTWAGG-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 7
- 210000004379 membrane Anatomy 0.000 description 147
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 57
- 239000002904 solvent Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 230000006378 damage Effects 0.000 description 13
- 241000894007 species Species 0.000 description 9
- 230000004913 activation Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241001558496 Talpa caeca Species 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000427 antigen Substances 0.000 description 2
- 102000036639 antigens Human genes 0.000 description 2
- 108091007433 antigens Proteins 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 102000006410 Apoproteins Human genes 0.000 description 1
- 108010083590 Apoproteins Proteins 0.000 description 1
- 102000014914 Carrier Proteins Human genes 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- 102000004856 Lectins Human genes 0.000 description 1
- 108090001090 Lectins Proteins 0.000 description 1
- 241000100287 Membras Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QPMSXSBEVQLBIL-CZRHPSIPSA-N ac1mix0p Chemical compound C1=CC=C2N(C[C@H](C)CN(C)C)C3=CC(OC)=CC=C3SC2=C1.O([C@H]1[C@]2(OC)C=CC34C[C@@H]2[C@](C)(O)CCC)C2=C5[C@]41CCN(C)[C@@H]3CC5=CC=C2O QPMSXSBEVQLBIL-CZRHPSIPSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 108091008324 binding proteins Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000002523 lectin Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000009871 nonspecific binding Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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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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- 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
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
- B01J20/3274—Proteins, nucleic acids, polysaccharides, antibodies or antigens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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- B01J20/3276—Copolymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/544—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being organic
- G01N33/545—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
Abstract
POLYALDEHYDE ACTIVATED MEMBRANES
ABSTRACT
An activated microporous membrane is provided, having aldehyde functional groups on its inner and outer sur-faces. The aldehyde functionality on all surfaces pro-vides for effective covalent bonding to the membrane by amine containing materials. The activated membrane can be made of a polysulfone/polyacrolein mixture or a polysulfone microporous membrane treated with a poly-acrolein solution.
GELM:129/C1
ABSTRACT
An activated microporous membrane is provided, having aldehyde functional groups on its inner and outer sur-faces. The aldehyde functionality on all surfaces pro-vides for effective covalent bonding to the membrane by amine containing materials. The activated membrane can be made of a polysulfone/polyacrolein mixture or a polysulfone microporous membrane treated with a poly-acrolein solution.
GELM:129/C1
Description
~77~
GELM:129 POLYALDEHYDE ACTIVATED MEMBRANES
This invention relates generally to chemically~
activated microporous membranes. More particularly, this invention relates to polyaldehyde activated microporous membranes and a process for making the same.
Aldehydes have been used in conjunction with a variety of materials, such as beads and microspheres. In addition, substrates including certain membranes have been chemically activated with aldehyde functional groups using methods such as oxidation.
Microporous membranes are also known. The tradi-tional use of microporous membranes to filter materials has been based mainly on their physical properties, e.g., pore size, thickness, strength, etc. For example, reten tion by microfiltration membranes is accomplished mainly through mechanical sieving. Even in uses where the chemical properties of a membrane come into play, such as in gas separation or desalination, generally chemical bonding between the separated species and the membrane matrix is not employed.
~k -2- 1 ~17 7 1i~
A type of microporous membrane which is capable of reacting chemically with soluble or suspended species is the so-called "affinity membrane." Various affinity membranes are commercially available. Some, which are designed to interact specifically with only one or a few species in complicated mixtures, are improvements over traditional membranes which rely on physical separations.
Examples of such highly specific interactions include antigen/antibody, hapten/antibody, apoprotein/cofactor and lectin/carbohydrate. Affinity membranes may be used in immunodiagnostic testing wherein the interaction between the antigen and antibody is particularly relevant.
But the currently available affinity membranes have certain drawbacks. For some, shelf life is limited because the active groups are destroyed by prolonged exposure to the atmosphere. For others, binding capacity is limited. Nonspecific binding, which can lead to false positive readings, is a problem as well. Nonspecific covalent binding is typically remedied by treating the membrane with a blocking agent. However, blocking agents do not always solve the problem satisfactorily.
There are also various shortcomings in the methods for making activated membranes. ~or example, some of the methods are limited to certain substrates or membrane polymers. An oxidation reaction, for example, is limited to membranes such as cellulose acetate, and would not activate other commercial membranes such as polysulfone, nylon or polypropylene. Also other chemical reactions may damage the pore structure of certain species of micro-porous membranes. In still others, clogging of the pores may present a problem.
35The drawbacks and shortcomings mentioned above illustrate some of the unsatisfactory characteristics of -3- 13177~
currently available affinity membranes and the need for further improvements in the art.
The present invention is directed to an activated microporous membrane and a process for making an activated microporous membrane. In a broad aspect, the invention includes an activated microporous membrane that comprises a membrane polymer and a polyaldehyde. The membrane polymer is physically activated with a mixture that contains polyaldehyde. A sufficient amount of polyaldehyde is combined with the membrane polymer to provide for effective covalent bonding with amine containing materials and other aldehyde reactive materials.
Various membranes of the present invention demon-strate e~cellent binding capacity, specificity and sensi-tivity. Without being bound to any particular theory, the effective binding capacity of the present membrane is believed to be due in part to the aldehyde functional groups which are attached to both the inner and outer surfaces of the microporous membrane. "Sensitivity"
re~ers to the ability of the membrane to detect even small amounts 3f bound or attached species. "Specificity" means the ability of the membrane to selectively bind or filter certain species from complex mixtures.
A practical advantage of the present invention is that membranes can be produced that are reactive enough to react with typical nucleophiles such as amines but not so reactive that they suffer degradation by ambient moisture or oxygen. Thus, one aspect of the invention provides a membrane which has not only a hi~h binding capacity and improved sensitivity but also a prolonged shelf life and ease of handling.
GELM:129 POLYALDEHYDE ACTIVATED MEMBRANES
This invention relates generally to chemically~
activated microporous membranes. More particularly, this invention relates to polyaldehyde activated microporous membranes and a process for making the same.
Aldehydes have been used in conjunction with a variety of materials, such as beads and microspheres. In addition, substrates including certain membranes have been chemically activated with aldehyde functional groups using methods such as oxidation.
Microporous membranes are also known. The tradi-tional use of microporous membranes to filter materials has been based mainly on their physical properties, e.g., pore size, thickness, strength, etc. For example, reten tion by microfiltration membranes is accomplished mainly through mechanical sieving. Even in uses where the chemical properties of a membrane come into play, such as in gas separation or desalination, generally chemical bonding between the separated species and the membrane matrix is not employed.
~k -2- 1 ~17 7 1i~
A type of microporous membrane which is capable of reacting chemically with soluble or suspended species is the so-called "affinity membrane." Various affinity membranes are commercially available. Some, which are designed to interact specifically with only one or a few species in complicated mixtures, are improvements over traditional membranes which rely on physical separations.
Examples of such highly specific interactions include antigen/antibody, hapten/antibody, apoprotein/cofactor and lectin/carbohydrate. Affinity membranes may be used in immunodiagnostic testing wherein the interaction between the antigen and antibody is particularly relevant.
But the currently available affinity membranes have certain drawbacks. For some, shelf life is limited because the active groups are destroyed by prolonged exposure to the atmosphere. For others, binding capacity is limited. Nonspecific binding, which can lead to false positive readings, is a problem as well. Nonspecific covalent binding is typically remedied by treating the membrane with a blocking agent. However, blocking agents do not always solve the problem satisfactorily.
There are also various shortcomings in the methods for making activated membranes. ~or example, some of the methods are limited to certain substrates or membrane polymers. An oxidation reaction, for example, is limited to membranes such as cellulose acetate, and would not activate other commercial membranes such as polysulfone, nylon or polypropylene. Also other chemical reactions may damage the pore structure of certain species of micro-porous membranes. In still others, clogging of the pores may present a problem.
35The drawbacks and shortcomings mentioned above illustrate some of the unsatisfactory characteristics of -3- 13177~
currently available affinity membranes and the need for further improvements in the art.
The present invention is directed to an activated microporous membrane and a process for making an activated microporous membrane. In a broad aspect, the invention includes an activated microporous membrane that comprises a membrane polymer and a polyaldehyde. The membrane polymer is physically activated with a mixture that contains polyaldehyde. A sufficient amount of polyaldehyde is combined with the membrane polymer to provide for effective covalent bonding with amine containing materials and other aldehyde reactive materials.
Various membranes of the present invention demon-strate e~cellent binding capacity, specificity and sensi-tivity. Without being bound to any particular theory, the effective binding capacity of the present membrane is believed to be due in part to the aldehyde functional groups which are attached to both the inner and outer surfaces of the microporous membrane. "Sensitivity"
re~ers to the ability of the membrane to detect even small amounts 3f bound or attached species. "Specificity" means the ability of the membrane to selectively bind or filter certain species from complex mixtures.
A practical advantage of the present invention is that membranes can be produced that are reactive enough to react with typical nucleophiles such as amines but not so reactive that they suffer degradation by ambient moisture or oxygen. Thus, one aspect of the invention provides a membrane which has not only a hi~h binding capacity and improved sensitivity but also a prolonged shelf life and ease of handling.
-4- ~31771~
In one aspect, the membrane of this invention is polymeric and microporous, i.e., it includes a polymer and has an internal surface and an external surface. When the activated microporous membrane of the invention is con-tacted with a mixture that is to be filtered, the externalportion of the membrane is immediately and directly exposed to the mixture. But the internal surface or interstices of the membrane are not immediately exposed.
It is only after the membrane has been in contact with the mixture for a period of time that the internal surface is exposed to the mixture. These internal interstices or pore surfaces are collectively termed the "internal surface" of the membrane. This internal surface area has been found to be important to the success of the invention.
In one aspect, the activated membranes of this invention have a plurality of aldehyde functional groups substantially covering the internal and external surfaces.
The interstices as well as the external surfaces are covered by an effective amount of aldehyde for activating the membrane. The number of aldehyde groups is sufficient for effective covalent bonding with amine containing materials and other aldehyde reactive groups.
The following detailed description describes the claimed invention in greater detail and discloses the preferred embodiment. The description, along with the examples and the rest of this disclosure, is addressed specifically to those skilled in the art~ to enable them to make and to use the claimed invention.
In a broad aspect, the invention includes an acti-vated microporous membrane that comprises a membrane polymer and a polyaldehyde. The polyaldehyde is physically combined with the membrane polymer in an amount 13177~
sufficient to activate the membrane, i.e., to provide for effective covalent bonding by amine containing materials and other aldehyde reactive materials.
"Activating" or "combining" in this sense is a broad term that encompasses both (a) coating or treating a pre-cast microporous membrane with the polyaldehyde; and (b) physically mixing the polyaldehyde with the membrane polymer before casting the membrane. The former is called "membrane post treatment" while the latter is called "precasting." "Physically combining" or "physically mixing" the polymer and the polyaldehyde means that there is a lack of significant chemical reaction between the polyaldehyde and the polymer.
In one specific embodiment, the invention comprises an activated microporous membrane in which substantially all the available surfaces of the membrane are coated by the polyaldehyde. The activated membrane thus contains sufficient polyaldehyde to provide effective aldehyde functionality on substantially all available surfaces, i.e., both the external and internal surfaces. The resulting free aldehyde groups covering substantially all exposed surface areas provide effective covalent bonding between the finished membrane of this invention and aldehyde reactive materials, such as amines, which contact the membrane.
In one embodiment, the membrane is a "supported"
membrane. Other embodiments include unsupported mem-branes. A supported membrane is a membrane cast on a substrate, preferably a nonwoven fabric. Supported membranes are often considered to have better mechanical properties and ease of handling than unsupported mem-branes.
-6- ~3~
Generally, the polyaldehyde is dissolved in a solvent to form a mixture. The mixture is then physically combined with the membrane polymer by either membrane post treatment or precasting. After the activated microporous membrane is made, the solvent is generally removed by washing, although some residual solvent may remain.
In certain embodiments, the polyaldehyde mixture is concentrated enough to properly activate the membrane.
The membrane material, on the other hand, is sturdy and of sufficient chemical resistance to remain porous and substantially undamaged by the polyaldehyde containing mixture.
Membrane Post Treatment In the preferred embodiment, the microporous membrane is first cast from the membrane polymer, then activated by physically coating or treating the cast membrane with the polyaldehyde containing mixture~ This physical combina-tion does not include any significant chemical reaction, such that would cause potential damage to the pore structure.
Polyaldehydes in general are contemplated for use in this invention. Preferably, the polyaldehyde chosen will be sufficiently soluble in the solvent to provide a true solution to avoid, for example, undesirable dispersions which could cause ineffective coating of the membrane surfaces. Polyaldehydes which have been found especially useful in the practice of the invention include polyacrolein and acrolein copolymers.
It has been found that the concentration of the solvent, in which the polyaldehyde dissolves, i5 important. If the solvent is not concentrated enough, it _7_ 1 3 ~1. rd ~
will not form a true solutlon with the polyaldehyde. If the solvent is too concentrated, it could damage the membrane pore structure oE certain membranes.
Accordingly, the solvent concentration should be reduced to avoid damaging the membrane. This can be done by diluting the solvent concentration with, for example, water or alcohol, which will reduce the solvent concentra-tion yet still dissolve the polyaldehyde.
Where polyacrolein is employed, a strong solvent such as pyridine or dimethyl formamide (DMF) is used to dissolve the polyacrolein. One embodiment of the post treatment mode comprises a microporous membrane treated with pure polyacrolein dissolved in DMF or pyridine. At high concentrations DMF or pyridine damages the pore structure of polysulfone. Accordingly, for polysulfone, an effective DMF solution in a polyacrolein containing mixture has about 60 percent DMF and about 40 percent water. Example 6 shows one operative range of DMF solvent concentrations. Other membrane polymers, such as those made from nylon or polypropylene, are generally not sensitive to pore damage and can be successfully coated - with polyacrolein without regard to the solvent concentration.
One polyaldehyde which has been found to work well with polysulfone membranes is a copolymer of acrolein, e.g., hydroxyethyl methacrylate acrolein copolymer. This copolymer is more soluble in solvents such as DMF and pyridine than is pure polyacrolein. Thus a less concentrated solvent can be used to avoid any potential damage to the membrane pore structure.
The proportionate amounts of polyaldehyde and solvent are also important. Enough polyaldehyde should be present to sufficiently activate the membrane. Further, enough -8- 13 ~
solvent must be employed to dissolve the polyaldehyde. It is contemplated that from about 0.2 weight percent to about 10 weight percent polyaldehyde per volume of solution is adequate.
Precastinq Treatment Another embodiment provides for the activation of the membrane polymer prior to casting. This may be referred to as the precasting treatment. In this embodiment, the polyaldehyde and the membrane polymer are physically mixed before casting. There should be sufficient polyaldehyde to activate the membrane polymer. With polyacrolein, weight ratios of from about 1:5 to about 1:1 polyacrolein to membrane polymer are appropriate.
The invention is not strictly limited to a particular species of microporous membrane. However, selection of an appropriate membrane polymer is important to achieve maximum effectiveness. Generally speaking, the species of membrane polymer must be able to withstand the solvent system that comprises the polyaldehyde. Examples of suitable membrane polymers include polysulfone and polyacrylonitrate-vinyl chloride copolymer. Other membranes, such as nylon, cellulose acetate, polyvinylidene fluoride, polypropylene, and glass fibers, could also be expected to work.
Membrane materials which would swell or dissolve from contact with the polyaldehyde containing mixture are undesirable. However, this depends to some extent on the concentration of the solvent used for the polyaldehyde.
For example, concentrated DMF on a polysulfone membrane causes damage to the membrane. Consequently, it is preferable to use a more soluble polyaldehyde such as a copolymer of acrolein and hydroxyethyl methacrylate with 9 ~ ~3 1 ~
polysulfone microporous membrane. No significant damage of polysulfone membrane pore structure has been encountered with this copolymer solvent system.
Polvmerization Polymerization conditions are also important. For example, under certain conditions polymerization will involve the aldehyde group of acrolein, and the resulting polymer will therefore have very little, if any, aldehyde functionality.
Where a polyaldehyde copolymer is formed between an acrolein monomer and hydroxyethyl methacrylate, free radical copolymerization is preferred, using a proper conventional initiator such as peroxide. In contrast, if the reaction is done under the influence of base-catalyzed initiators, such as sodium hydroxide, few if any free aldehydes are formed. Likewise, if ionizing radiation is used, microspheres will be formed, which may not be able to penetrate all interstices of the porous membrane.
Generally, the preferred polymerization conditions are those which provide a highly soluble and highly functional polymer mixture that will cover the microporous membrane efficiently and without damage to or clogging of the pore structure. The polyaldehyde of the present invention is soluble enough in solutions having solvents such as DMF or pyridine to penetrate substantially all pores or interstices of the microporous membrane structure.
In one embodiment of this invention, the aldehyde functional groups are attached by admixing the membrane polymer with an effective amount of the polyaldehyde-containing mixture. Generally speaking, the type and -lo- 1 317 ~ ~
amount of polyaldehyde containing mixture vary the binding effectiveness of the membrane. These are discussed below.
A preferred embodiment which has good solubility but which does not damage the pore structure of a polysulfone membrane is an acrolein copolymer. However, incorporation of a comonomer with acrolein may somewhat reduce the concentration of the reactive aldehyde groups. Accord-ingly, selection of the comonomer is important. A good balance of solubility and high reactivity is found with the copolymers of acrolein and hydroxyethyl methacrylate.
The Process 15Another broad aspect of the invention is the process for making the activated microporous membrane, which basically comprises an activating step and a casting step.
More particularly, the activating step refers to activat-ing the membrane polymer by mixing, treating or combining a polyaldehyde with the membrane polymer. The castiny step comprises casting the microporous membrane itself which includes the membrane polymer.
The actual method for casting microporous membranes is conventional. In the preferred embodiment, the casting step is performed first. Here, the microporous membrane matrix is cast from a membrane polymer system, which may include polymers such as polysulfone, polyacrylonitrile-vinyl chloride, nylon, polyvinylidene fluoride and poly-propylene. The matrix may also include glass fibers.Preferably, the pore sizes of the microporous membrane are between about 0.1 and about lO microns in diameter. These have been found sufficiently porous for most applications.
35After the casting of the membrane, the activating or treating step is performed. Here, the polyaldehyde is 3 :~ ~ 7 ~ ~
physically combined with the cast microporous membrane.
Preferably, a dilute solution of the polyaldehyde containing mixture ic made in a solvent that is not harmful to the membrane polymer system. A harmful solvent S is generally one that would increase the solubility of the membrane to a point where it would damage the membrane by causing the pore structure to collapse. As discussed above, the preferred solvent is an aqueous D~F solution having at most about 60~ DMF. Pyridine may also be used as a solvent.
One of the embodiments includes copolymerizing acrolein with hydroxyethyl methacrylate to obtain a copolymer, then mixing with a solvent to obtain a mixture having the appropriate concentration and solubility. The membrane is dipped in this mixture in a manner ensuring proper wetting of all surfaces, internal and external.
Once dried, the membrane is ready for use.
In another embodiment of this process, the activating step is performed first. In this embodiment, the polyaldehyde is physically mixed with the microporous polymer prior to casting. A polyaldehyde containing mixture is physically mixed with a membrane polymer in the proper proportions. Using this mixture, a membrane matrix is cast in a conventional manner. When the membrane has undergone transition from a liquid or sol phase to a solid or gel phase and subsequently dried, the pore surfaces of the membrane will have aldehyde functionalities available for reaction.
The following reaction steps illustrate how acrolein is polymerized. As indicated, acrolein can be polymerized either through the aldehyde group or the carbon-carbon double bond, depending on polymerization conditions.
-12- ~l311 7 ~3 ~
2,CH CH2 0}~- - C~- O -C - O -- I
",~C' --CH2 ~ CH - C
R~
-- C~2 - CH - CH2 - CH ---H" ~ C~ II
The resulting polymer is therefore one having either pendant vinyl (I) or aldehyde (II) groups. Polymer II is suitable for a cast membrane in the presence of a solvent system or alternatively for blending in a membrane forming mix so as to activate the membrane before casting. As discussed above, it is preferable to improve the solu-bility of the aldehyde polymer so that a larger variety of membranes can be treated.
The activated microporous membrane can be used in a variety of applications. It is particularly effective as a binding matrix. Various amine containing macromolecules will attach to it covalently. The membrane can therefore be used for selectively binding proteins, nucleic acids and other nucleophiles. The bound species can then be used in a variety of uses such as catalysis and analysis.
The invention will be further clarified by a consid-eration of the following examples, which are intended to be purely exemplary of the use of the invention.
-13- 13:!L77~1 ~
EXAMPLES
EXAMPLE 1:
Polymerization of Acrolein:
A mixture containing freshly distilled acrolein ~50 ml, 0.749 moles), benzoyl peroxide (2g, 8.2b m.moles) and 250 ml of dimethyl formamide (DMF) was purged for 3 hours with nitrogen at room temperature. Then the mixture was heated to 70-80C for 2 hours with stirring. The resulting solution was stirred at room temperature for 15 hours. A yellowish homogeneous solution was obtained.
This solution was diluted with water to obtain poly-acrolein as a white precipitate. Polyacrolein was redis-solved in pyridine and stored at room temperature for usein Example 2.
EXAMPLE 2:
Activation of a Membrane By Coating a Polysulfone Microporous Membrane with Polyacrolein Mixture:
The polyacrolein/pyridine solution of Example l was heated to 70C and diluted with l volume of boiling water.
This polyacrolein containing mixture was applied on a polysulfone microporous membrane at 70C and dried at room temperature in air. No sign of clearing (destruction of porous structure) of the membrane was observed by the above treatment. This indicated that the mixture solvent was not too strong.
-14- 1 ~ 77~ ~
EX~LE 3:
Activation of a Membrane by Precasting with a Polyacrolein Mixture:
The polyacrolein/DMF solution in Example 1 was mixed with polysulfone to precast a microporous membrane. The casting mix was prepared by blending 30 g of the polyacrolein solution, 10 ml of additional DMF, 10 g of polyethylene glycol, 1.5 g of polyvinyl pyrrolidinone, and 8.5 g of polysulfone. The mix was cast on a glass plate at room temperature and stored in a humidity chamber to cause pore formation. The microporous membrane produced by this method exh bited a water flow rate of 6.8 sec/100 ml/9.62 cm and a water bubble point of 18 psi.
This indicated that the membrane was microporous and possessed an adequate pore structure.
EXAMPLE 4:
Copolymerization ~f Acrolein and Hydroxyethyl Methacrylate:
Hydroxyethyl methacrylate acrolein copolymer was dissolved in DMF and diluted with water. One such mixture was made in the following manner. A mixture consisting of freshly distilled acrolein (50 ml, 0.749 moles), hydroxyethyl methacrylate (15 ml, 0.12 moles~ benzoyl peroxide (3.25 g, 13.4 m.moles) and 200 ml of DMF was purged with nitrogen Eor 1 hour and then refluxed for 1 hour. The resulting mixture was stirred at room temperature for 15 hours. A yellow copolymer solution was obtained. This copolymer solution was diluted with 1.5 volume of water without any solidification.
-15- ~ 3 ~ 7 7 ~ /~
EXAMPLE 5:
Activation of a Polysulfone Membrane By Coating a Microporous Membrane with a Copolymer Mixture:
S The copolymer solution of Example 4 was heated to 70C and diluted with 1.5 volumes of water at 70C. This copolymer solution was applied on a supported microporous polysulfone membrane at room temperature and dried in air at room temperature. No sign of clearing of the membrane was observed by this treatment. Further, the supported polysulfone membrane exhibited a water flow rate of 13.5 sec/100 ml/9.62 cm after the above treatment. This indicated that the hydroxyethyl methacrylate acrolein copolymer mixture did not significantly damage the pore lS structure of the microporous membrane.
EXAMPLE 6:
Copolymerization of Acrolein and Hydroxyethyl Methacrylate:
In order to demonstrate the usefulness of this invention with different membranes, a second copolymer mixture was made and applied to a polysulfone microporous membrane and an acrylonitrile/vinyl chloride copolymer microporous membrane.
First, a mixture of freshly distilled acrolein (265 ml, 3.97 moles), hydroxyethyl methacrylate (62 ml, 0.49 moles), benzoyl peroxide (17 g, 70 m.moles) and DMF
(1060 ml) was purged with N2 gas for 6 hours. This mixture was then heated to 95C for 22 hrs. The final concentration of the copolymer was 17.5% (w/v). A brown copolymer solution was stored at room temperature for membrane post treatment.
-16- 1 3 ~ 7 7 ~ ~
EXAMPLE 7:
Activation of Polysulfone and Polyacrylonitrile-Vinyl Chloride Microporous Membranes by Coatinq:
The copolymer solution in Example 6 was diluted with a mixture of 1:1:1 DMF/water/isopropanol to form various copolymer solutions including 0.5%, 1%, 2~, 3~, 4~ and 5%
(w/v) solutions. These copolymer solutions were applied to a polysulfone microporous membrane and a polyacrylo-nitrile-vinyl chloride membrane.
The membranes were quenched in deionized water, washed a few times with deionized water, and dried at 70C. The flow rates of two of the membranes, i.e., those treated with the 4% solution, were measured. It was found that the water flow rates of the membranes were reduced.
For instances, the flow rate of the treated polysulfone membrane was reduced from 10.7 sec/100 ml/9.62 cm2/S72 mm Hg to 13.1 sec/100 ml/9.62 cm2/572 mm Eg. This reduction in flow rates indicated that the internal surfaces of the membranes were coated. The flow rates of the treated membranes are found in Table 1. The binding capacities of these membranes are shown in Example 8.
Table 1.
Water Flow Rates of Composite Membranes Water Flow Rat~
Membrane sec/100 ml/9.2 cm ~572 mm Hq Polysulfone membrane coated with 13.1 aldehyde polymer in Example 7.
Acrylonitrile/vinyl chloride 16.6 copolymer supported membrane coated with aldehyde polymer in Example 7.
-17- 1 3 ~ 7 ~ 1~
EXAMPLE 8:
As demonstrated by the following data, several embodiments of this invention showed excellent binding capacities.
Table 20 2 Total Protein Binding Capacity (ug/cm ) of the Membranes by ELISA
Total Binding2 Membra~e Capacity (ua/cm ) Polysulfone membrane coated with aldehyde 96 15 polymer in Example 7.
Acrylonitrile/vinyl chloride copolymer 106 supported membrane co~a~d with aldehyde polymer in Example 7.
(a) 2-1/4 hr. binding time at 35C.
EXAMPLE 9:
Another embodiment of the invention comprising glyoxyl agarose polyaldehyde, was made to demonstrate the further usefulness of the invention. A solution was prepared, mixing 0.5 g glyoxyl agarose (NuFix~
manufactured by FMC Corporation) in 200 ml of boiling water. The solution was used to treat a polysulfone membrane in the same manner as in Example 5. It was observed that the flow properties of the membrane remained unchanged indicating that the pore structure remained essentially undamaged.
~31~7~
-18~
1 EXAMPLE 10:
As demonstrated by the following data, the membranes of this invention showed specificity and binding capacity that was superior to other commercially available membranes. Commercial Affinity Membrane A was a nylon-based membrane sold by Pall Corporation under the trade mark ~IODYNE. Commercial Affinity Membrane B was a polyvinylidene difluoride-based membrane sold by Millipore Corp. under t~e trade mark IMMOBILON.
' '-;, r -lg- 131~7~
Table 3.
Total Binding Capacities (ug/cm2) of Membranes by BCA Method 5 (Total binding capacity = covalent or permanently bound protein + loos~ly bound or noncovalent bound protein per cm ~
.
Non-Covalently Total Binding 2 Bound Pro~ein MembraneCapac~ty (uq/cm ) (ug~_m ) Commercial Affinity 57 10 Membrane A
Commercial Affinity 42 Not Detectable (10) Membrane B
Nitrocellulose(a)94 64 25 Polysulfone Membrane 120 Not Detectable (10) Coated with Aldehyde (b Polymer, from Example 5 30 Polysulfone/Aldehyde 90 Not Detectable tlO) Polymer Microporous (a Membrane in Example 7 35 Polysulfone Supported 125 5.2 Membrane Coated with Aldehyde ~D~ymer in Example 7 Polysulfone Membrane 148 3.4 Coated with Aldehyde(b Polymer in Example 7 Polysulfone Membrane 87 Coated with Aldehyde Polymer in Example 2 .. . . _ .
~ 317 rl 3~ f~
(a) 1 hour binding time at room temperature.
(b) 1 hour binding time at 60C.
(c) 3 hours binding time at room temperature.
(d) 3.45 hours binding time at room temperature.
These binding capacities were determined according to the BCA method, developed by P.K. Smith, et. al., Analytical B chemistry, 150, pase 76 (1985).
In one aspect, the membrane of this invention is polymeric and microporous, i.e., it includes a polymer and has an internal surface and an external surface. When the activated microporous membrane of the invention is con-tacted with a mixture that is to be filtered, the externalportion of the membrane is immediately and directly exposed to the mixture. But the internal surface or interstices of the membrane are not immediately exposed.
It is only after the membrane has been in contact with the mixture for a period of time that the internal surface is exposed to the mixture. These internal interstices or pore surfaces are collectively termed the "internal surface" of the membrane. This internal surface area has been found to be important to the success of the invention.
In one aspect, the activated membranes of this invention have a plurality of aldehyde functional groups substantially covering the internal and external surfaces.
The interstices as well as the external surfaces are covered by an effective amount of aldehyde for activating the membrane. The number of aldehyde groups is sufficient for effective covalent bonding with amine containing materials and other aldehyde reactive groups.
The following detailed description describes the claimed invention in greater detail and discloses the preferred embodiment. The description, along with the examples and the rest of this disclosure, is addressed specifically to those skilled in the art~ to enable them to make and to use the claimed invention.
In a broad aspect, the invention includes an acti-vated microporous membrane that comprises a membrane polymer and a polyaldehyde. The polyaldehyde is physically combined with the membrane polymer in an amount 13177~
sufficient to activate the membrane, i.e., to provide for effective covalent bonding by amine containing materials and other aldehyde reactive materials.
"Activating" or "combining" in this sense is a broad term that encompasses both (a) coating or treating a pre-cast microporous membrane with the polyaldehyde; and (b) physically mixing the polyaldehyde with the membrane polymer before casting the membrane. The former is called "membrane post treatment" while the latter is called "precasting." "Physically combining" or "physically mixing" the polymer and the polyaldehyde means that there is a lack of significant chemical reaction between the polyaldehyde and the polymer.
In one specific embodiment, the invention comprises an activated microporous membrane in which substantially all the available surfaces of the membrane are coated by the polyaldehyde. The activated membrane thus contains sufficient polyaldehyde to provide effective aldehyde functionality on substantially all available surfaces, i.e., both the external and internal surfaces. The resulting free aldehyde groups covering substantially all exposed surface areas provide effective covalent bonding between the finished membrane of this invention and aldehyde reactive materials, such as amines, which contact the membrane.
In one embodiment, the membrane is a "supported"
membrane. Other embodiments include unsupported mem-branes. A supported membrane is a membrane cast on a substrate, preferably a nonwoven fabric. Supported membranes are often considered to have better mechanical properties and ease of handling than unsupported mem-branes.
-6- ~3~
Generally, the polyaldehyde is dissolved in a solvent to form a mixture. The mixture is then physically combined with the membrane polymer by either membrane post treatment or precasting. After the activated microporous membrane is made, the solvent is generally removed by washing, although some residual solvent may remain.
In certain embodiments, the polyaldehyde mixture is concentrated enough to properly activate the membrane.
The membrane material, on the other hand, is sturdy and of sufficient chemical resistance to remain porous and substantially undamaged by the polyaldehyde containing mixture.
Membrane Post Treatment In the preferred embodiment, the microporous membrane is first cast from the membrane polymer, then activated by physically coating or treating the cast membrane with the polyaldehyde containing mixture~ This physical combina-tion does not include any significant chemical reaction, such that would cause potential damage to the pore structure.
Polyaldehydes in general are contemplated for use in this invention. Preferably, the polyaldehyde chosen will be sufficiently soluble in the solvent to provide a true solution to avoid, for example, undesirable dispersions which could cause ineffective coating of the membrane surfaces. Polyaldehydes which have been found especially useful in the practice of the invention include polyacrolein and acrolein copolymers.
It has been found that the concentration of the solvent, in which the polyaldehyde dissolves, i5 important. If the solvent is not concentrated enough, it _7_ 1 3 ~1. rd ~
will not form a true solutlon with the polyaldehyde. If the solvent is too concentrated, it could damage the membrane pore structure oE certain membranes.
Accordingly, the solvent concentration should be reduced to avoid damaging the membrane. This can be done by diluting the solvent concentration with, for example, water or alcohol, which will reduce the solvent concentra-tion yet still dissolve the polyaldehyde.
Where polyacrolein is employed, a strong solvent such as pyridine or dimethyl formamide (DMF) is used to dissolve the polyacrolein. One embodiment of the post treatment mode comprises a microporous membrane treated with pure polyacrolein dissolved in DMF or pyridine. At high concentrations DMF or pyridine damages the pore structure of polysulfone. Accordingly, for polysulfone, an effective DMF solution in a polyacrolein containing mixture has about 60 percent DMF and about 40 percent water. Example 6 shows one operative range of DMF solvent concentrations. Other membrane polymers, such as those made from nylon or polypropylene, are generally not sensitive to pore damage and can be successfully coated - with polyacrolein without regard to the solvent concentration.
One polyaldehyde which has been found to work well with polysulfone membranes is a copolymer of acrolein, e.g., hydroxyethyl methacrylate acrolein copolymer. This copolymer is more soluble in solvents such as DMF and pyridine than is pure polyacrolein. Thus a less concentrated solvent can be used to avoid any potential damage to the membrane pore structure.
The proportionate amounts of polyaldehyde and solvent are also important. Enough polyaldehyde should be present to sufficiently activate the membrane. Further, enough -8- 13 ~
solvent must be employed to dissolve the polyaldehyde. It is contemplated that from about 0.2 weight percent to about 10 weight percent polyaldehyde per volume of solution is adequate.
Precastinq Treatment Another embodiment provides for the activation of the membrane polymer prior to casting. This may be referred to as the precasting treatment. In this embodiment, the polyaldehyde and the membrane polymer are physically mixed before casting. There should be sufficient polyaldehyde to activate the membrane polymer. With polyacrolein, weight ratios of from about 1:5 to about 1:1 polyacrolein to membrane polymer are appropriate.
The invention is not strictly limited to a particular species of microporous membrane. However, selection of an appropriate membrane polymer is important to achieve maximum effectiveness. Generally speaking, the species of membrane polymer must be able to withstand the solvent system that comprises the polyaldehyde. Examples of suitable membrane polymers include polysulfone and polyacrylonitrate-vinyl chloride copolymer. Other membranes, such as nylon, cellulose acetate, polyvinylidene fluoride, polypropylene, and glass fibers, could also be expected to work.
Membrane materials which would swell or dissolve from contact with the polyaldehyde containing mixture are undesirable. However, this depends to some extent on the concentration of the solvent used for the polyaldehyde.
For example, concentrated DMF on a polysulfone membrane causes damage to the membrane. Consequently, it is preferable to use a more soluble polyaldehyde such as a copolymer of acrolein and hydroxyethyl methacrylate with 9 ~ ~3 1 ~
polysulfone microporous membrane. No significant damage of polysulfone membrane pore structure has been encountered with this copolymer solvent system.
Polvmerization Polymerization conditions are also important. For example, under certain conditions polymerization will involve the aldehyde group of acrolein, and the resulting polymer will therefore have very little, if any, aldehyde functionality.
Where a polyaldehyde copolymer is formed between an acrolein monomer and hydroxyethyl methacrylate, free radical copolymerization is preferred, using a proper conventional initiator such as peroxide. In contrast, if the reaction is done under the influence of base-catalyzed initiators, such as sodium hydroxide, few if any free aldehydes are formed. Likewise, if ionizing radiation is used, microspheres will be formed, which may not be able to penetrate all interstices of the porous membrane.
Generally, the preferred polymerization conditions are those which provide a highly soluble and highly functional polymer mixture that will cover the microporous membrane efficiently and without damage to or clogging of the pore structure. The polyaldehyde of the present invention is soluble enough in solutions having solvents such as DMF or pyridine to penetrate substantially all pores or interstices of the microporous membrane structure.
In one embodiment of this invention, the aldehyde functional groups are attached by admixing the membrane polymer with an effective amount of the polyaldehyde-containing mixture. Generally speaking, the type and -lo- 1 317 ~ ~
amount of polyaldehyde containing mixture vary the binding effectiveness of the membrane. These are discussed below.
A preferred embodiment which has good solubility but which does not damage the pore structure of a polysulfone membrane is an acrolein copolymer. However, incorporation of a comonomer with acrolein may somewhat reduce the concentration of the reactive aldehyde groups. Accord-ingly, selection of the comonomer is important. A good balance of solubility and high reactivity is found with the copolymers of acrolein and hydroxyethyl methacrylate.
The Process 15Another broad aspect of the invention is the process for making the activated microporous membrane, which basically comprises an activating step and a casting step.
More particularly, the activating step refers to activat-ing the membrane polymer by mixing, treating or combining a polyaldehyde with the membrane polymer. The castiny step comprises casting the microporous membrane itself which includes the membrane polymer.
The actual method for casting microporous membranes is conventional. In the preferred embodiment, the casting step is performed first. Here, the microporous membrane matrix is cast from a membrane polymer system, which may include polymers such as polysulfone, polyacrylonitrile-vinyl chloride, nylon, polyvinylidene fluoride and poly-propylene. The matrix may also include glass fibers.Preferably, the pore sizes of the microporous membrane are between about 0.1 and about lO microns in diameter. These have been found sufficiently porous for most applications.
35After the casting of the membrane, the activating or treating step is performed. Here, the polyaldehyde is 3 :~ ~ 7 ~ ~
physically combined with the cast microporous membrane.
Preferably, a dilute solution of the polyaldehyde containing mixture ic made in a solvent that is not harmful to the membrane polymer system. A harmful solvent S is generally one that would increase the solubility of the membrane to a point where it would damage the membrane by causing the pore structure to collapse. As discussed above, the preferred solvent is an aqueous D~F solution having at most about 60~ DMF. Pyridine may also be used as a solvent.
One of the embodiments includes copolymerizing acrolein with hydroxyethyl methacrylate to obtain a copolymer, then mixing with a solvent to obtain a mixture having the appropriate concentration and solubility. The membrane is dipped in this mixture in a manner ensuring proper wetting of all surfaces, internal and external.
Once dried, the membrane is ready for use.
In another embodiment of this process, the activating step is performed first. In this embodiment, the polyaldehyde is physically mixed with the microporous polymer prior to casting. A polyaldehyde containing mixture is physically mixed with a membrane polymer in the proper proportions. Using this mixture, a membrane matrix is cast in a conventional manner. When the membrane has undergone transition from a liquid or sol phase to a solid or gel phase and subsequently dried, the pore surfaces of the membrane will have aldehyde functionalities available for reaction.
The following reaction steps illustrate how acrolein is polymerized. As indicated, acrolein can be polymerized either through the aldehyde group or the carbon-carbon double bond, depending on polymerization conditions.
-12- ~l311 7 ~3 ~
2,CH CH2 0}~- - C~- O -C - O -- I
",~C' --CH2 ~ CH - C
R~
-- C~2 - CH - CH2 - CH ---H" ~ C~ II
The resulting polymer is therefore one having either pendant vinyl (I) or aldehyde (II) groups. Polymer II is suitable for a cast membrane in the presence of a solvent system or alternatively for blending in a membrane forming mix so as to activate the membrane before casting. As discussed above, it is preferable to improve the solu-bility of the aldehyde polymer so that a larger variety of membranes can be treated.
The activated microporous membrane can be used in a variety of applications. It is particularly effective as a binding matrix. Various amine containing macromolecules will attach to it covalently. The membrane can therefore be used for selectively binding proteins, nucleic acids and other nucleophiles. The bound species can then be used in a variety of uses such as catalysis and analysis.
The invention will be further clarified by a consid-eration of the following examples, which are intended to be purely exemplary of the use of the invention.
-13- 13:!L77~1 ~
EXAMPLES
EXAMPLE 1:
Polymerization of Acrolein:
A mixture containing freshly distilled acrolein ~50 ml, 0.749 moles), benzoyl peroxide (2g, 8.2b m.moles) and 250 ml of dimethyl formamide (DMF) was purged for 3 hours with nitrogen at room temperature. Then the mixture was heated to 70-80C for 2 hours with stirring. The resulting solution was stirred at room temperature for 15 hours. A yellowish homogeneous solution was obtained.
This solution was diluted with water to obtain poly-acrolein as a white precipitate. Polyacrolein was redis-solved in pyridine and stored at room temperature for usein Example 2.
EXAMPLE 2:
Activation of a Membrane By Coating a Polysulfone Microporous Membrane with Polyacrolein Mixture:
The polyacrolein/pyridine solution of Example l was heated to 70C and diluted with l volume of boiling water.
This polyacrolein containing mixture was applied on a polysulfone microporous membrane at 70C and dried at room temperature in air. No sign of clearing (destruction of porous structure) of the membrane was observed by the above treatment. This indicated that the mixture solvent was not too strong.
-14- 1 ~ 77~ ~
EX~LE 3:
Activation of a Membrane by Precasting with a Polyacrolein Mixture:
The polyacrolein/DMF solution in Example 1 was mixed with polysulfone to precast a microporous membrane. The casting mix was prepared by blending 30 g of the polyacrolein solution, 10 ml of additional DMF, 10 g of polyethylene glycol, 1.5 g of polyvinyl pyrrolidinone, and 8.5 g of polysulfone. The mix was cast on a glass plate at room temperature and stored in a humidity chamber to cause pore formation. The microporous membrane produced by this method exh bited a water flow rate of 6.8 sec/100 ml/9.62 cm and a water bubble point of 18 psi.
This indicated that the membrane was microporous and possessed an adequate pore structure.
EXAMPLE 4:
Copolymerization ~f Acrolein and Hydroxyethyl Methacrylate:
Hydroxyethyl methacrylate acrolein copolymer was dissolved in DMF and diluted with water. One such mixture was made in the following manner. A mixture consisting of freshly distilled acrolein (50 ml, 0.749 moles), hydroxyethyl methacrylate (15 ml, 0.12 moles~ benzoyl peroxide (3.25 g, 13.4 m.moles) and 200 ml of DMF was purged with nitrogen Eor 1 hour and then refluxed for 1 hour. The resulting mixture was stirred at room temperature for 15 hours. A yellow copolymer solution was obtained. This copolymer solution was diluted with 1.5 volume of water without any solidification.
-15- ~ 3 ~ 7 7 ~ /~
EXAMPLE 5:
Activation of a Polysulfone Membrane By Coating a Microporous Membrane with a Copolymer Mixture:
S The copolymer solution of Example 4 was heated to 70C and diluted with 1.5 volumes of water at 70C. This copolymer solution was applied on a supported microporous polysulfone membrane at room temperature and dried in air at room temperature. No sign of clearing of the membrane was observed by this treatment. Further, the supported polysulfone membrane exhibited a water flow rate of 13.5 sec/100 ml/9.62 cm after the above treatment. This indicated that the hydroxyethyl methacrylate acrolein copolymer mixture did not significantly damage the pore lS structure of the microporous membrane.
EXAMPLE 6:
Copolymerization of Acrolein and Hydroxyethyl Methacrylate:
In order to demonstrate the usefulness of this invention with different membranes, a second copolymer mixture was made and applied to a polysulfone microporous membrane and an acrylonitrile/vinyl chloride copolymer microporous membrane.
First, a mixture of freshly distilled acrolein (265 ml, 3.97 moles), hydroxyethyl methacrylate (62 ml, 0.49 moles), benzoyl peroxide (17 g, 70 m.moles) and DMF
(1060 ml) was purged with N2 gas for 6 hours. This mixture was then heated to 95C for 22 hrs. The final concentration of the copolymer was 17.5% (w/v). A brown copolymer solution was stored at room temperature for membrane post treatment.
-16- 1 3 ~ 7 7 ~ ~
EXAMPLE 7:
Activation of Polysulfone and Polyacrylonitrile-Vinyl Chloride Microporous Membranes by Coatinq:
The copolymer solution in Example 6 was diluted with a mixture of 1:1:1 DMF/water/isopropanol to form various copolymer solutions including 0.5%, 1%, 2~, 3~, 4~ and 5%
(w/v) solutions. These copolymer solutions were applied to a polysulfone microporous membrane and a polyacrylo-nitrile-vinyl chloride membrane.
The membranes were quenched in deionized water, washed a few times with deionized water, and dried at 70C. The flow rates of two of the membranes, i.e., those treated with the 4% solution, were measured. It was found that the water flow rates of the membranes were reduced.
For instances, the flow rate of the treated polysulfone membrane was reduced from 10.7 sec/100 ml/9.62 cm2/S72 mm Hg to 13.1 sec/100 ml/9.62 cm2/572 mm Eg. This reduction in flow rates indicated that the internal surfaces of the membranes were coated. The flow rates of the treated membranes are found in Table 1. The binding capacities of these membranes are shown in Example 8.
Table 1.
Water Flow Rates of Composite Membranes Water Flow Rat~
Membrane sec/100 ml/9.2 cm ~572 mm Hq Polysulfone membrane coated with 13.1 aldehyde polymer in Example 7.
Acrylonitrile/vinyl chloride 16.6 copolymer supported membrane coated with aldehyde polymer in Example 7.
-17- 1 3 ~ 7 ~ 1~
EXAMPLE 8:
As demonstrated by the following data, several embodiments of this invention showed excellent binding capacities.
Table 20 2 Total Protein Binding Capacity (ug/cm ) of the Membranes by ELISA
Total Binding2 Membra~e Capacity (ua/cm ) Polysulfone membrane coated with aldehyde 96 15 polymer in Example 7.
Acrylonitrile/vinyl chloride copolymer 106 supported membrane co~a~d with aldehyde polymer in Example 7.
(a) 2-1/4 hr. binding time at 35C.
EXAMPLE 9:
Another embodiment of the invention comprising glyoxyl agarose polyaldehyde, was made to demonstrate the further usefulness of the invention. A solution was prepared, mixing 0.5 g glyoxyl agarose (NuFix~
manufactured by FMC Corporation) in 200 ml of boiling water. The solution was used to treat a polysulfone membrane in the same manner as in Example 5. It was observed that the flow properties of the membrane remained unchanged indicating that the pore structure remained essentially undamaged.
~31~7~
-18~
1 EXAMPLE 10:
As demonstrated by the following data, the membranes of this invention showed specificity and binding capacity that was superior to other commercially available membranes. Commercial Affinity Membrane A was a nylon-based membrane sold by Pall Corporation under the trade mark ~IODYNE. Commercial Affinity Membrane B was a polyvinylidene difluoride-based membrane sold by Millipore Corp. under t~e trade mark IMMOBILON.
' '-;, r -lg- 131~7~
Table 3.
Total Binding Capacities (ug/cm2) of Membranes by BCA Method 5 (Total binding capacity = covalent or permanently bound protein + loos~ly bound or noncovalent bound protein per cm ~
.
Non-Covalently Total Binding 2 Bound Pro~ein MembraneCapac~ty (uq/cm ) (ug~_m ) Commercial Affinity 57 10 Membrane A
Commercial Affinity 42 Not Detectable (10) Membrane B
Nitrocellulose(a)94 64 25 Polysulfone Membrane 120 Not Detectable (10) Coated with Aldehyde (b Polymer, from Example 5 30 Polysulfone/Aldehyde 90 Not Detectable tlO) Polymer Microporous (a Membrane in Example 7 35 Polysulfone Supported 125 5.2 Membrane Coated with Aldehyde ~D~ymer in Example 7 Polysulfone Membrane 148 3.4 Coated with Aldehyde(b Polymer in Example 7 Polysulfone Membrane 87 Coated with Aldehyde Polymer in Example 2 .. . . _ .
~ 317 rl 3~ f~
(a) 1 hour binding time at room temperature.
(b) 1 hour binding time at 60C.
(c) 3 hours binding time at room temperature.
(d) 3.45 hours binding time at room temperature.
These binding capacities were determined according to the BCA method, developed by P.K. Smith, et. al., Analytical B chemistry, 150, pase 76 (1985).
Claims (13)
1. An affinity membrane comprising:
a microporous polymeric membrane matrix with available surface areas including an internal surface area comprising internal pore surfaces and internal interstices, and an external surface area; and polyaldehyde having physically bound aldehyde functional groups which are thus bound without significant chemical reaction to substantially all said available surface areas, said polyaldehyde further having unbound aldehyde groups that are free to react with and have an affinity for aldehyde reactive materials, said unbound polyaldehyde groups being in an amount such that the affinity of the membrane for protein is characterized by enhanced specificity and total binding capacity.
a microporous polymeric membrane matrix with available surface areas including an internal surface area comprising internal pore surfaces and internal interstices, and an external surface area; and polyaldehyde having physically bound aldehyde functional groups which are thus bound without significant chemical reaction to substantially all said available surface areas, said polyaldehyde further having unbound aldehyde groups that are free to react with and have an affinity for aldehyde reactive materials, said unbound polyaldehyde groups being in an amount such that the affinity of the membrane for protein is characterized by enhanced specificity and total binding capacity.
2. An activated polymeric microporous membrane as recited in claim 1 wherein the pore surfaces have free aldehyde functionalities available for affinity reaction.
3. A membrane as recited in claim 1 wherein the matrix is a supported matrix.
4. A membrane as recited in claim 1 wherein the matrix is a supported matrix and the polyaldehyde is selected from the group consisting of aldehyde-agarose, polyacrolein, and acrolein copolymer.
5. A membrane as recited in claim 1 wherein the matrix comprises polysulfone and the polyaldehyde is a copolymer of acrolein and hydroxyethyl methacrylate.
6. A membrane as recited in claim 1 having a total binding capacity of at least about 10 ug/cm2 based on the outer surface area of the membrane.
7. A process for making an activated microporous membrane comprising:
casting a microporous membrane that comprises a membrane polymer; and activating the membrane polymer by physically combining a polyaldehyde containing mixture with the membrane polymer in an amount sufficient to cover substantially all available surface area of the microporous membrane.
casting a microporous membrane that comprises a membrane polymer; and activating the membrane polymer by physically combining a polyaldehyde containing mixture with the membrane polymer in an amount sufficient to cover substantially all available surface area of the microporous membrane.
8. A process as recited in claim 7 wherein the activating step follows the casting step; and the activating step comprises physically treating the membrane with a polyaldehyde containing mixture.
9. A process as recited in claim 7 wherein:
the activating step precedes the casting step;
the activating step comprises physically mixing the polyaldehyde containing mixture with the membrane polymer in an amount sufficient to activate the membrane; and the casting step comprises casting a microporous membrane from the mixture of the membrane polymer and the polyaldehyde containing mixture.
the activating step precedes the casting step;
the activating step comprises physically mixing the polyaldehyde containing mixture with the membrane polymer in an amount sufficient to activate the membrane; and the casting step comprises casting a microporous membrane from the mixture of the membrane polymer and the polyaldehyde containing mixture.
10. A process as recited in claim 7 wherein the membrane is a supported membrane and comprises a membrane polymer selected from the group consisting of polysulfone, acrylonitrile-vinyl chloride copolymer, nylon and propylene.
11. A process as recited in claim 7 wherein the polyaldehyde containing mixture includes polyacrolein or a copolymer of acrolein and hydroxyethyl methacrylate.
12. A process for making an activated microporous membrane comprising:
casting a microporous membrane from a first mixture that includes a member selected from the group consisting of polysulfone, acrylonitrile vinyl chloride, nylon and polypropylene; and activating the membrane by physically mixing with the first mixture a second mixture that includes a member selected from the group consisting of polyacrolein and a copolymer of acrolein and hydroxyethyl methacrylate.
casting a microporous membrane from a first mixture that includes a member selected from the group consisting of polysulfone, acrylonitrile vinyl chloride, nylon and polypropylene; and activating the membrane by physically mixing with the first mixture a second mixture that includes a member selected from the group consisting of polyacrolein and a copolymer of acrolein and hydroxyethyl methacrylate.
13. A process as recited in claim 12 wherein physically mixing the first mixture to the second mixture includes either post treating the cast membrane or mixing the first mixture and the second mixture before casting.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/096,730 US4824870A (en) | 1987-09-14 | 1987-09-14 | Polyaldehyde activated membranes |
US096,730 | 1987-09-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1317714C true CA1317714C (en) | 1993-05-18 |
Family
ID=22258815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA000576838A Expired - Fee Related CA1317714C (en) | 1987-09-14 | 1988-09-08 | Polyaldehyde activated membranes |
Country Status (7)
Country | Link |
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US (1) | US4824870A (en) |
EP (1) | EP0308206B1 (en) |
JP (1) | JP2837167B2 (en) |
AT (1) | ATE104568T1 (en) |
CA (1) | CA1317714C (en) |
DE (1) | DE3889184T2 (en) |
ES (1) | ES2055739T3 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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US4992172A (en) * | 1987-09-14 | 1991-02-12 | Gelman Sciences, Inc. | Blotting methods using polyaldehyde activated membranes |
US5250443A (en) * | 1988-11-23 | 1993-10-05 | Pb Diagnostic Systems, Inc. | Biological diagnostic assay system |
US5215882A (en) * | 1989-11-30 | 1993-06-01 | Ortho Diagnostic Systems, Inc. | Method of immobilizing nucleic acid on a solid surface for use in nucleic acid hybridization assays |
DE59107131D1 (en) * | 1990-07-10 | 1996-02-01 | Sartorius Gmbh | POROUS, NON-PARTICULAR AND CONVECTIVE PERMEABLE MATRIX |
US5131927A (en) * | 1991-04-22 | 1992-07-21 | Union Carbide Industrial Gases Technology Corporation | Reactive treatment of composite gas separation membranes |
US5344701A (en) * | 1992-06-09 | 1994-09-06 | Minnesota Mining And Manufacturing Company | Porous supports having azlactone-functional surfaces |
US5476665A (en) * | 1994-04-13 | 1995-12-19 | Minnesota Mining And Manufacturing Company | Azlactone functional particles incorporated in a membrane formed by solvent phase inversion |
US5547760A (en) * | 1994-04-26 | 1996-08-20 | Ibc Advanced Technologies, Inc. | Compositions and processes for separating and concentrating certain ions from mixed ion solutions using ion-binding ligands bonded to membranes |
US5510421A (en) * | 1994-05-26 | 1996-04-23 | Minnesota Mining And Manufacturing Company | Azlactone-functional membranes and methods of preparing and using same |
US6544418B1 (en) | 1996-10-31 | 2003-04-08 | University Of Kentucky Research Foundation | Preparing and regenerating a composite polymer and silica-based membrane |
US6139742A (en) * | 1996-10-31 | 2000-10-31 | University Of Kentucky Research Foundation | Membrane-based sorbent for heavy metal sequestration |
US6103121A (en) * | 1996-10-31 | 2000-08-15 | University Of Kentucky Research Foundation | Membrane-based sorbent for heavy metal sequestration |
US6306301B1 (en) | 1996-10-31 | 2001-10-23 | University Of Kentucky Research Foundation | Silica-based membrane sorbent for heavy metal sequestration |
US6045899A (en) * | 1996-12-12 | 2000-04-04 | Usf Filtration & Separations Group, Inc. | Highly assymetric, hydrophilic, microfiltration membranes having large pore diameters |
US6306665B1 (en) | 1999-10-13 | 2001-10-23 | A-Fem Medical Corporation | Covalent bonding of molecules to an activated solid phase material |
US6699722B2 (en) | 2000-04-14 | 2004-03-02 | A-Fem Medical Corporation | Positive detection lateral-flow apparatus and method for small and large analytes |
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FR2115595A5 (en) * | 1970-11-25 | 1972-07-07 | Inst Textile De France | Ion exchange resin - comprising pva graft copolymer insolubilised by acetailisation |
US3977941A (en) * | 1971-04-20 | 1976-08-31 | Research Corporation | Protein-enzyme complex membranes |
CH533139A (en) * | 1971-06-21 | 1973-01-31 | Nestle Sa | Process for preparing a product endowed with enzymatic activity, insoluble in aqueous medium |
US3770588A (en) * | 1972-10-02 | 1973-11-06 | American Cyanamid Co | Storage stabilization of carrier bound enzymes |
CA1056746A (en) * | 1974-09-06 | 1979-06-19 | Chung J. Lai | Biologically active membrane material |
JPS54110385A (en) * | 1978-02-13 | 1979-08-29 | Toyobo Co Ltd | Immobilization of enzyme |
US4255591A (en) * | 1978-11-20 | 1981-03-10 | Monsanto Company | Carbonylation process |
DE2967545D1 (en) * | 1979-06-11 | 1985-12-19 | Gambro Lundia Ab | A device for removal of substances from a liquid |
US4238204A (en) * | 1979-06-18 | 1980-12-09 | Monsanto Company | Selective adsorption process |
US4229188A (en) * | 1979-06-18 | 1980-10-21 | Monsanto Company | Selective adsorption process |
US4299537A (en) * | 1979-06-19 | 1981-11-10 | Evans Frederick C | Interlinked variable-pitch blades for windmills and turbines |
US4279787A (en) * | 1979-07-30 | 1981-07-21 | Tetra Consultants Inc. | Method of binding antigens to insoluble polymeric substances |
JPS56115727A (en) * | 1980-02-19 | 1981-09-11 | Kuraray Co Ltd | Carrier for immobilizing physiologically active substance |
JPS56141559A (en) * | 1980-04-04 | 1981-11-05 | Toray Ind Inc | Reagent for immunological inspection |
US4357142A (en) * | 1980-07-18 | 1982-11-02 | Akzona Incorporated | Glass support coated with synthetic polymer for bioprocess |
US4363634A (en) * | 1980-07-18 | 1982-12-14 | Akzona Incorporated | Glass support coated with synthetic polymer for bioprocess |
US4438239A (en) * | 1981-03-30 | 1984-03-20 | California Institute Of Technology | Microsphere coated substrate containing reactive aldehyde groups |
JPS5850522B2 (en) * | 1981-03-31 | 1983-11-11 | 日東電工株式会社 | Composite semipermeable membrane and its manufacturing method |
US4351711A (en) * | 1981-04-21 | 1982-09-28 | Gelman Sciences, Inc. | Electrophoresis method for detecting glycosylated hemoglobin in blood |
ATE42317T1 (en) * | 1983-07-29 | 1989-05-15 | Henning Berlin Gmbh | PRE-ACTIVATED PLASTIC SURFACES FOR IMMOBILIZATION OF ORGANIC CHEMICAL AND BIOLOGICAL MATERIALS, PROCESS FOR THE MANUFACTURE AND USE OF SAME. |
US4511478A (en) * | 1983-11-10 | 1985-04-16 | Genetic Systems Corporation | Polymerizable compounds and methods for preparing synthetic polymers that integrally contain polypeptides |
US4624923A (en) * | 1984-06-08 | 1986-11-25 | Yeda Research And Development Company Limited | Metal-coated polyaldehyde microspheres |
JPS6157628A (en) * | 1984-08-27 | 1986-03-24 | Nok Corp | Production of physiologically active substance immobilized film |
-
1987
- 1987-09-14 US US07/096,730 patent/US4824870A/en not_active Expired - Lifetime
-
1988
- 1988-09-08 CA CA000576838A patent/CA1317714C/en not_active Expired - Fee Related
- 1988-09-13 JP JP63229697A patent/JP2837167B2/en not_active Expired - Lifetime
- 1988-09-14 AT AT8888308509T patent/ATE104568T1/en not_active IP Right Cessation
- 1988-09-14 DE DE3889184T patent/DE3889184T2/en not_active Expired - Fee Related
- 1988-09-14 EP EP88308509A patent/EP0308206B1/en not_active Expired - Lifetime
- 1988-09-14 ES ES88308509T patent/ES2055739T3/en not_active Expired - Lifetime
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JP2837167B2 (en) | 1998-12-14 |
US4824870A (en) | 1989-04-25 |
DE3889184D1 (en) | 1994-05-26 |
JPH01158054A (en) | 1989-06-21 |
EP0308206A2 (en) | 1989-03-22 |
EP0308206A3 (en) | 1990-01-10 |
ATE104568T1 (en) | 1994-05-15 |
ES2055739T3 (en) | 1994-09-01 |
DE3889184T2 (en) | 1994-10-20 |
EP0308206B1 (en) | 1994-04-20 |
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