Supports having azlactone-functional surfaces, adduct supports, and methods of preparing both

• US 5,451,453 A
• Filed: 06/20/1994
• Issued: 09/19/1995
• Est. Priority Date: 06/09/1992
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Rasmussen, Jerald K., Lyons, Christopher S., Coleman, Patrick L., Kwon, Oh-Seung, Milbrath, Dean S., Drtina, Gary J., Gagnon, David R., Stahl, Julie B.
• Primary Examiner(s): BERMAN, SUSAN W
• Application Number:
  US08/262,738
• Time in Patent Office: 456 Days
• Field of Search: 428/304.4, 428/308.4, 428/308.8, 428/315.5, 428/319.3, 522/116, 522/136, 522/173, 522/87, 522/88, 522/89, 522/138, 525/54.1, 525/63, 525/279, 525/300
• US Class Current: 428/305.5
• CPC Class Codes: A61L 33/0011 Anticoagulant, e.g. heparin, platelet aggregation inhibitor, fibrinolytic agent, other than enzymes, attached to the substrate
• CPC Class Codes: B01J 20/28023 Fibres or filaments fibres or filaments in the form of membranes B01J20/28038; B01J20/28007 takes precedence
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/321 consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3212 consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3219 involving a particular spacer or linking group, e.g. for attaching an active group
• CPC Class Codes: B01J 20/3255 comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
• CPC Class Codes: B01J 20/3274 Proteins, nucleic acids, polysaccharides, antibodies or antigens
• CPC Class Codes: B01J 20/3276 Copolymers
• CPC Class Codes: B01J 20/3278 Polymers being grafted on the carrier
• CPC Class Codes: B01J 20/328 Polymers on the carrier being further modified
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: C07K 17/08 the carrier being a synthetic polymer
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C12N 11/082 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C12N 11/084 Polymers containing vinyl alcohol units
• CPC Class Codes: C12N 11/087 Acrylic polymers
• CPC Class Codes: G01N 33/54353 : with ligand attached to the carrier via a chemical coupling agent coatings G01N33/54393
• CPC Class Codes: Y10T 428/249953 : Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249954 : With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/249958 : Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249959 : Void-containing component is wood or paper
• CPC Class Codes: Y10T 428/249978 : Voids specified as micro
• CPC Class Codes: Y10T 428/249991 : Synthetic resin or natural rubbers

Abstract

Supports having azlactone-functional surfaces, adduct supports prepared from such azlactone-functional supports, and methods of preparing both are disclosed. Azlactone functionality is introduced to surfaces of a pre-existing support in a manner which retains useful physical and chemical characteristics of the pre-existing support. One method involves exposing surfaces with high energy radiation to generate free radical reaction sites on the surfaces and causing azlactone-functional moieties to react with the free radical reaction sites. Another method involves coating surfaces with azlactone monomers, crosslinking monomers, and optionally co-monomers and polymerizing the monomers to form a polymerized coating of azlactone-functionality on the surfaces. Another method involves dispersion polymerization of azlactone-functional moieties to produce azlactone-functional particles within pores and interstices of a pre-existing support. Adduct supports are formed by coupling nucleophilic reagents, such as biologically active materials, to azlactone-functional moieties of the support.

Claims

1. An adduct support, comprising:

a chemically reactive support having azlactone-functionality at surfaces of the support and a ligand comprising a nucleophilic reagent reacted with the azlactone-functionality, wherein the chemically reactive support comprises a porous pre-existing support having surfaces and azlactone-functional moieties contacting only the surfaces and modifying reactivity of only such surfaces while retaining useful porosity of the pre-existing support;

wherein said contacting is selected from the group consisting of chemically grafting the azlactone-functional moieties to the surfaces, crosslinking the azlactone-functional moieties in a coating over the surfaces, and forming crosslinked particles of the azlactone-functional moieties in contact with the surfaces.

2. The adduct support according to claim 1, wherein the azlactone-functional moieties comprise oxazolinone moieties of the formula:

##STR4## wherein R¹ and R² independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon atoms and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and

n is an integer 0 or 1.

3. The adduct support according to claim 1, wherein the pre-existing support is a ceramic, glassy, metallic, or polymeric material.

4. The adduct support according to claim 3, wherein the pre-existing support is a polymeric material.

5. The adduct support according to claim 4, wherein the porous, polymeric material is a woven web, a nonwoven web, a microporous fiber, or a microporous membrane.

6. The adduct support according to claim 1, wherein the nucleophilic reagent comprises biologically active materials, acids, bases, chelators, hydrophiles, lipophiles, hydrophobes, zwitterions, detergents, or combinations thereof.

7. The adduct support according to claim 6, wherein biologically active material comprises substances which are biologically, immunochemically, physiologically, or pharmaceutically active.

8. The adduct support according to claim 7, wherein the biologically active material comprises proteins, peptides, polypeptides, antibodies, antigenic substances, enzymes, cofactors, inhibitors, lectins, hormones, receptors, coagulation factors, amino acids, histones, vitamins, drugs, cell surface markers, substances which interact with them, or combinations thereof.

9. The adduct support according to claim 6, wherein the adduct support is an adsorbant, complexing agent, catalyst, or chromatographic article.

10. The adduct support according to claim 6, wherein the adduct support is a mammalian body implant and wherein the nucleophilic reagent is an anticoagulant.