Synthesis and Characterization of Copolymers containing N,N-dimethylacrylamide and 2-vinyl-4,4’-dimethylazlactone

Stanek, Lee G.; Heilmann, Steven M.; Gleason, William B.

doi:10.1007/s00289-005-0450-x

Cited by 6 publications

(6 citation statements)

References 22 publications

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“…It was found the VDMA is preferentially incorporated into the copolymer for all seven comonomer pairs (Table 2). This is consistent with current literature that reports preferential incorporation of VDMA with DMAA15, MPEG 300 MA12, MMA14, BA7, and styrene17.…”

Section: Resultssupporting

confidence: 93%

“…4(b)], reflecting very similar r 1 and r 2 values (see Supporting Information for separate r values). The resulting combined reactivity ratios ( r 1 (VDMA) = 2.13 and r 2 (DMAA) = 0.17) differ from the values reported by Stanek et al ( r 2 (VDMA) = 0.7 and r 2 (DMAA) = 0.3),15 and do not point to the azeotropic behavior that was observed by Stanek et al at a VDMA mol fraction 0.78. Stanek et al used thermally initiated polymerization in methylethylketone at 70 °C, while we used room temperature photo‐polymerization in DMSO and in situ tracking of monomer conversion by 1 H NMR.…”

Section: Resultscontrasting

confidence: 83%

“…6 VDMA contains the electrophilic azlactone ring that can rapidly react with amines, alcohols, and thiols in a ring-opening reaction under mild conditions, to form amide, ester, and thioester bonds, respectively, 7 without formation of any small molecule byproducts. VDMA is readily polymerized by both conventional and controlled free radical polymerizations, [8][9][10][11][12] incorporating preferentially during copolymerization with methacrylic acid (MAA), 13 methyl methacrylate (MMA), 14 N,N-dimethylacrylamide, 15 vinyl pyrrolidone, 16 butyl acrylate (BA), 7 and styrene. 17 The majority of VDMA-based polymers have been used to prepare thin films 18,19 and to immobilize proteins and other biorelevant molecules onto solid polymer supports.…”

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confidence: 99%

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Synthesis and properties of water‐soluble azlactone copolymers

Gardner

Brown

Stöver

2012

J. Polym. Sci. A Polym. Chem.

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Preparation and study of a series of copolymers incorporating 2-vinyl-4,4-dimethylazlactone (VDMA) is reported. The reactivity ratios for photo-initiated free radical copolymerization of VDMA with methacrylic acid (MAA), acrylic acid (AA), acrylamide (AAm), dimethylacrylamide (DMAA), hydroxyethyl methacrylate (HEMA), methoxy poly(ethylene glycol) methacrylate (MPEG 300 MA), and 2-methacryloyloxyethyl phosphorylcholine (MPC), were determined by fitting comonomer conversion data obtained by in situ 1 H NMR to a terminal copolymerization equation. Semi-batch photo-copolymerizations were then used to synthesize the corresponding VDMA copolymers with constant composition. Their solubility and dissolution behavior, as well as their hydrolysis half-lives under physiological conditions, were determined. P(VDMA-co-MAA) copolymers with 52 to 93 mol % VDMA showed decreasing initial solubility and increasing hydrolysis half-lives with increasing VDMA content. VDMA copolymers with nonionic monomers AAm and DMAA were water soluble only at VDMA contents of 41 and 22 mol % or less, respectively, and showed longer hydrolysis half-lives than comparable MAA copolymers. VDMA copolymers with HEMA and MPEG 300 MA were found to crosslink during storage, so their hydrolysis half-lives were not determined. VDMA copolymers with 18% zwitterionic MPC showed a much longer half-life and superior initial solubility compared to analogous p(VDMAco-MAA), identifying this copolymer as a promising candidate for macromolecular crosslinkers in, for example, aqueous layerby-layer co-depositions with polyamines. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: [4674][4675][4676][4677][4678][4679][4680][4681][4682][4683][4684][4685] 2012

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Section: Resultssupporting

confidence: 93%

Section: Resultscontrasting

confidence: 83%

mentioning

confidence: 99%

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Synthesis and properties of water‐soluble azlactone copolymers

Gardner

Brown

Stöver

2012

J. Polym. Sci. A Polym. Chem.

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“…Most of the published work, including the preparations of cross-linked thin films using a layer-by-layer approach, has been carried out in organic media, as the VDMA homopolymer is not soluble in water. VDMA has been shown to incorporate preferentially during copolymerization with methyl methacrylate, N,N -dimethylacrylamide, vinylpyrrolidone, butyl acrylate, and styrene in organic solvents . To date, VDMA has not been copolymerized with an acidic comonomer or used to form LBL assemblies with polycations in aqueous conditions.…”

Section: Introductionmentioning

confidence: 99%

Reactive Polyanions Based on Poly(4,4-dimethyl-2-vinyl-2-oxazoline-5-one-co-methacrylic acid)

Gardner

Stöver

2011

Macromolecules

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The formation of reactive polyanions by semibatch copolymerization of 4,4-dimethyl-2-vinyl-2-oxazoline-5one (VDMA) and methacrylic acid (MAA) by both free radical and photoinduced radical polymerization is described. The reactivity ratios of these two monomers were determined to be 1.36 and 0.41 for r 1 (VDMA) and r 2 (MAA), respectively, using 1 H NMR spectroscopy. During the free radical copolymerization of a 50:50 VDMA:MAA copolymer (PMV 50 ) in anhydrous DMSO or THF at 60 °C, up to 40% of the azlactone groups in the copolymer are hydrolyzed by water formed largely by conversion of methacrylic acid diads into cyclic anhydride. Storage in organic solutions leads to further transhydration, while solid PMV 50 is stable for at least 6 months at room temperature. Increasing the VDMA comonomer content reduces this transhydration, likely through decreasing the incidence of methacrylic acid diads in the backbone. Alternatively, conducting the copolymerization at 20 °C using photoinitiation is also effective at suppressing this transhydration. The resulting reactive polyanions bind under physiological conditions to poly-L-lysine-coated calcium alginate hydrogel beads and spontaneously cross-link with the polyamine to form covalent networks of interest for long-term therapeutic cell encapsulation. This represents the first such use of a VDMA-containing polyanion in aqueous environments. The copolymers were characterized by 1 H NMR, quantitative 13 C NMR, 13 C DEPT-135 NMR, and FT-IR spectroscopies as well as by elemental analysis.

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“…Polymers containing VDMA are hydrolytically stable, and they form stable covalent bonds with amine and thiol groups commonly found in enzymes, proteins, and other biomolecules. , Nucleophilic addition of a primary amine proceeds without a catalyst and at room temperature, yielding a stable amide linkage. , This property has been exploited to immobilize proteins on polymers of VDMA in solution and to construct multilayered films via a layer-by-layer approach, reacting poly(vinyl dimethyl azlactone) (pVDMA) with poly(ethylene imine) in an alternating fashion . Despite reports showing that polymers incorporating VDMA can be made by free radical and controlled (free) radical polymerizations , and that proteins and other biomolecules can be immobilized onto pVDMA, ,,, thus far there have been no reports of using VDMA-based polymers as a surface-grafted platform to decorate interfaces with biomolecules.…”

Section: Introductionmentioning

confidence: 99%

Immobilization of Biomolecules on Poly(vinyldimethylazlactone)-Containing Surface Scaffolds

et al. 2008

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We describe the successful development of a procedure for the step-by-step formation of a reactive, multilayer polymer scaffold incorporating polymers based on 2-vinyl-4,4-dimethylazlactone (VDMA) on a silicon wafer and the characterization of these materials. Also discussed is the development of a procedure for the nonsite specific attachment of a biomolecule to a modified silicon wafer, including scaffolds modified via drop-on-demand (DOD) inkjet printing. VDMA-based polymers were used because of their hydrolytic stability and ability of the pendant azlactone rings to form stable covalent bonds with primary amines without byproducts via nucleophilic addition. This reaction proceeds without a catalyst and at room temperature, yielding a stable amide linkage, which adds to the ease of construction expected when using VDMA-based polymers. DOD inkjet printing was explored as an interesting method for creating surfaces with one or more patterns of biomolecules because of the flexibility and ease of pattern design.

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Synthesis and Characterization of Copolymers containing N,N-dimethylacrylamide and 2-vinyl-4,4’-dimethylazlactone

Cited by 6 publications

References 22 publications

Synthesis and properties of water‐soluble azlactone copolymers

Synthesis and properties of water‐soluble azlactone copolymers

Reactive Polyanions Based on Poly(4,4-dimethyl-2-vinyl-2-oxazoline-5-one-co-methacrylic acid)

Immobilization of Biomolecules on Poly(vinyldimethylazlactone)-Containing Surface Scaffolds

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