FUNCTIONAL SURFACES

Abstract

Articles having functional surfaces, for example antimicrobial functional surfaces, are prepared by methods comprising anodization. Organophosphorous compounds are deposited on a surface by methods comprising anodization, followed by attaching functional compounds, functional oligomers or functional polymers. Alternatively, functional organophosphorous compounds, functional oligomers or functional polymers are deposited on a surface by methods comprising anodization.

Claims

1.-28. (canceled)

29. A method for preparing an article having a functional surface, the method comprising: preparing a solution including an organophosphorous compound; placing the article having a metal surface in the solution; and depositing the organophosphorous compound on the metal surface via anodization, wherein the organophosphorous compound comprises an organophosphonic acid, an organophosphinic acid, or an organophosphoric acid, wherein the organophosphorous compound is modified by attaching one or more functional compounds, functional oligomers, or functional polymers to the organophosphorous layer to form a functional layer, and wherein the one or more functional compounds, functional oligomers, or functional polymers comprise a quaternary ammonium salt, a pyridinium salt, or a phosphonium salt.

30. The method of claim 29, wherein an organo group of the organophosphorous compound is a C.sub.2-C.sub.12 hydrocarbyl group.

31. The method of claim 29, wherein the metal surface comprises a surface comprising titanium, a titanium alloy, stainless steel, a cobalt chrome alloy, nickel, molybdenum, tantalum, zirconium, magnesium, or an alloy containing one or more of nickel, molybdenum, tantalum, zirconium, and magnesium.

32. The method of claim 29, wherein the metal surface comprises a titanium surface.

33. The method of claim 29, wherein an organo group of the organophosphorous compound is reacted with a diamine or an aminoalcohol to provide a distal amine which is subsequently quaternized to provide the functional layer comprising a quaternary ammonium compound.

34. The method of claim 29, wherein the organophosphorous compound is an unsaturated organophosphorous monomer, and wherein the unsaturated organophosphorous monomer is reacted with an unsaturated functional monomer to form the functional layer comprising one or more of the functional oligomers or the functional polymers.

35. The method of claim 34, wherein the unsaturated functional monomer is an antimicrobial monomer optionally comprising an ammonium salt, a pyridinium salt, or a phosphonium salt.

36. The method of claim 35, wherein the antimicrobial monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide.

37. The method of claim 34, wherein the unsaturated functional monomer comprises vinyl phosphonic acid, allyl phosphonic acid, 2-methyl allylphosphonic acid, 2-butenyl phosphonic acid, allyl phosphate, or ethyleneglycol methacrylatephosphate.

38. The method of claim 29, wherein in the modifying step, atom transfer radial polymerization of an unsaturated functional monomer is utilized to attach one or more of the functional oligomers or the functional polymers to the organophosphorous layer to form the functional layer.

39. The method of claim 38, wherein the unsaturated functional monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyloxyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide.

40. The method of claim 29, wherein the organophosphorous compound is covalently bonded to an oxide layer through phosphinate, phosphonate, or phosphate moieties.

41. The method of claim 29, wherein the depositing step comprises: connecting the metal surface to a positive terminal of an electric power supply; connecting a counter electrode placed in the solution to a negative electrode of the power supply; and applying a voltage for a predetermined period.

42. The method of claim 41, wherein the voltage ranges from about 1 to about 400 volts.

43. The method of claim 41, wherein the predetermined period ranges from about 1 to about 60 seconds.

44. The method of claim 29, wherein the article is a medical device.

45. The method of claim 29, wherein the solution is partially aqueous.

46. The method of claim 45, wherein the solution comprises an alcohol.

47. An article having a functional surface, the article prepared by the method of claim 29.

48. An article, comprising: a metal surface having a functional layer disposed thereon, wherein the functional layer comprises one or more functional compounds, functional oligomers, or functional polymers, wherein the one or more functional compounds, functional oligomers, or functional polymers comprise a quaternary ammonium salt, a pyridinium salt, or a phosphonium salt, and an organophosphorous compound deposited on the metal surface, wherein one or more functional compounds, functional oligomers, or functional polymers are attached to the organophosphorous compound.

49. The article of claim 48, wherein the organophosphorous compound comprises an organophosphonic acid, an organophosphinic acid, or an organophosphoric acid.

50. The article of claim 48, wherein an organo group of the organophosphorous compound is a C.sub.2-C.sub.12 hydrocarbyl group.

51. The article of claim 48, wherein the metal surface comprises a surface comprising titanium, a titanium alloy, stainless steel, a cobalt chrome alloy, nickel, molybdenum, tantalum, zirconium, magnesium, or an alloy containing one or more of nickel, molybdenum, tantalum, zirconium, and magnesium.

52. The article of claim 48, wherein the metal surface comprises a titanium surface.

53. The article of claim 48, an organo group of the organophosphorous compound is reacted with a diamine or an aminoalcohol to provide a distal amine which is subsequently quaternized to provide the functional layer comprising the quaternary ammonium compound.

54. The article of claim 48, wherein the organophosphorous compound is an unsaturated organophosphorous monomer, and wherein the unsaturated organophosphorous monomer is reacted with an unsaturated functional monomer to form the functional layer comprising one or more of the functional oligomers or the functional polymers.

55. The article of claim 54, wherein the unsaturated functional monomer is an antimicrobial monomer optionally comprising an ammonium salt, a pyridinium salt, or a phosphonium salt.

56. The article of claim 55, wherein the antimicrobial monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyloxyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide.

57. The article of claim 48, wherein the organophosphorous compound is covalently bonded to an oxide layer through phosphinate, phosphonate, or phosphate moieties.

58. The article of claim 48, wherein the organophosphorous compound is deposited on the metal surface via anodization.

59. The article of claim 48, wherein the article is a medical device.

Description

EXAMPLES

Example 1

Attachment of Antimicrobial Functional Polymers By Free-Radical Polymerization

[0113] A clean metal titanium strip is placed in a 15 weight % aqueous solution of vinyl phosphonic acid. A titanium counter electrode is attached to the negative terminal of a DC power supply. The voltage is adjusted to between 1 and 300V and a titanium rod connected to the positive terminal of the power supply is contacted with the titanium strip for a period of from 1 to 30 seconds.

[0114] Anodization occurs, resulting in formation of a titanium oxide layer and vinyl phosphonic acid bonded to the oxide layer via phosphonate moieties. Ti—O—P fragments are observed via TOF-SIMS surface analysis. The titanium surface having an attached unsaturated organophosphorus layer is represented as below.

##STR00001##

[0115] A solution of 12-methacryloyloxydodecylpyridinium bromide (MDPB) in ethanol (1 g/70 mL) is sprayed onto the titanium surface containing the vinylphosphonate layer (unsaturated organophosphorus layer). The titanium strips are placed in a nitrogen purged UV ozone cleaner chamber and exposed to UV light with a lambda max of ca. 260 nm with continuous purging for 15 minutes, resulting in polymerization of the vinyl groups with the methacrylate groups.

[0116] A titanium strip containing an antimicrobial layer is formed. The antimicrobial layer attached to a titanium surface contains an oxide layer, an organophosphorus layer and an antimicrobial polymer containing antimicrobial monomer units, as represented below, where * is a terminal end group.

##STR00002##

Example 2

Antimicrobial Efficacy

[0117] Titanium strips according to Example 1 and untreated samples are cut into 1×1 cm squares, sanitized with 70% alcohol and dried with argon. The sanitized samples are aseptically transferred individually into the wells of a sterile 24-well polystyrene dish. An overnight culture of MSSA 29213 is diluted in ASTM E2149 working buffer (0.3 mM KH.sub.2PO.sub.4, pH 7.2) to OD.sub.600=0.005 (˜1-4E+06 CFU/mL).

[0118] A 330 mL portion of the bacterial dilution is pipetted into each of the wells to cover the samples. A sample of the bacterial dilution is also serially diluted in 1× DPBS (Dulbecco's phosphate-buffered saline) and drop plated in triplicate on a TSA plate to ensure the bacterial challenge is on target. The TSA (tryptone soya agar) plates are incubated overnight at 37° C.

[0119] The polystyrene dish is placed into the 37° C. incubator at 500 RPM on a IKA MS3 digital shaker with a microtiter plate attachment overnight (18±2 hours). After the overnight incubation, the 24-well plate containing the sample buffer is removed from the incubator and the buffer samples are pipetted into a 96-well plate and serially diluted 1:10 in 1× DPBS. Each dilution is drop plated in triplicate for each sample on TSA plates. The plates are incubated overnight at 37° C. Against MSSA 21293, treated coupons show a reduction vs. control of 99.92% this assay.