Covalent Layer‐by‐Layer Assembly Using Reactive Polymers

Broderick, Adam H.; Lynn, David M.

doi:10.1002/9783527655427.ch15

Cited by 11 publications

(24 citation statements)

References 153 publications

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“…1–4 In contrast to conventional approaches to layer-by-layer assembly, which typically lead to multilayers assembled through multivalent weak interactions (e.g., ionic interactions, hydrogen bonding, etc. ), 5–9 reactive assembly leads to covalently crosslinked polymer films that are generally more stable in harsh media and chemically complex environments.…”

Section: Introductionmentioning

confidence: 99%

“…), 5–9 reactive assembly leads to covalently crosslinked polymer films that are generally more stable in harsh media and chemically complex environments. 1–4 This approach to assembly also leads to coatings that contain residual reactive functionality that can serve as a useful chemical ‘handle’ to immobilize additional functionality or tune bulk and interfacial properties. 1–4 The physical, chemical, and mechanical properties of these covalent assemblies, the extents to which they can be modified post-fabrication, the nature of the chemical crosslinks, and the conditions under which they remain stable or can be induced to degrade are all, in large measure, dependent upon the functional properties of the reactive building blocks used during fabrication and the nature of the reactive groups used to drive assembly.…”

Section: Introductionmentioning

confidence: 99%

“…1–4 This approach to assembly also leads to coatings that contain residual reactive functionality that can serve as a useful chemical ‘handle’ to immobilize additional functionality or tune bulk and interfacial properties. 1–4 The physical, chemical, and mechanical properties of these covalent assemblies, the extents to which they can be modified post-fabrication, the nature of the chemical crosslinks, and the conditions under which they remain stable or can be induced to degrade are all, in large measure, dependent upon the functional properties of the reactive building blocks used during fabrication and the nature of the reactive groups used to drive assembly. 1–4 A variety of reactive materials have been investigated to manipulate these variables, with the majority of past studies focused on the investigation of mutually reactive macromolecular building blocks to fabricate polymer/polymer-based multilayers of interest and potential utility in many different fundamental and applied contexts.…”

Section: Introductionmentioning

confidence: 99%

“…1–4 A variety of reactive materials have been investigated to manipulate these variables, with the majority of past studies focused on the investigation of mutually reactive macromolecular building blocks to fabricate polymer/polymer-based multilayers of interest and potential utility in many different fundamental and applied contexts. 1–4 …”

Section: Introductionmentioning

confidence: 99%

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Layer-by-Layer Assembly of Amine-Reactive Multilayers Using an Azlactone-Functionalized Polymer and Small-Molecule Diamine Linkers

2017

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We report the reactive layer-by-layer assembly of amine-reactive polymer multilayers using an azlactone-functionalized polymer and small-molecule diamine linkers. This approach yields crosslinked polymer/linker-type films that can be further functionalized, after fabrication, by treatment with functional primary amines, and provides opportunities to incorporate other useful functionality that can be difficult to introduce using other polyamine building blocks. Films fabricated using poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and three model non-degradable aliphatic diamine linkers yielded reactive thin films that were stable upon incubation in physiologically relevant media. In contrast, films fabricated using PVDMA and varying amounts of the model disulfide-containing diamine linker cystamine were stable in normal physiological media, but were unstable and eroded rapidly upon exposure to chemical reducing agents. We demonstrate that this approach can be used to fabricate functionalized polymer microcapsules that degrade in reducing environments, and that rates of erosion, extents of capsule swelling, and capsule degradation can be tuned by control over the relative concentration of cystamine linker used during fabrication. The polymer/linker approach used here expands the range of properties and functions that can be designed into reactive PVDMA-based coatings, including functionality that can degrade, erode, and undergo triggered destruction in aqueous environments. We therefore anticipate that these approaches will be useful for the functionalization, patterning, and customization of coatings, membranes, capsules, and interfaces of potential utility in biotechnical or biomedical contexts and other areas where degradation and transience are desired. The proof of concept strategies reported here are likely to be general, and should prove useful for the design of amine-reactive coatings containing other functional structures by judicious control of the structures of the linkers used during assembly.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Layer-by-Layer Assembly of Amine-Reactive Multilayers Using an Azlactone-Functionalized Polymer and Small-Molecule Diamine Linkers

2017

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“…11-14 The latter 'reactive' or 'covalent' approaches offer several potential practical advantages relative to methods that rely on assembly coordinated through weak interactions, including the fact that they lead to covalently crosslinked coatings that can exhibit enhanced physical and chemical stability in complex media. [11][12][13][14] In addition, the use of reactive polymers to drive assembly often yields reactive coatings that can be further functionalized to impart new surface or bulk properties after fabrication. Many different reactive polymers have been investigated with these goals in mind, 11-14 with the overall facility and extent to which physical stability, chemical reactivity, and other features can be exploited depending heavily upon the chemical nature of the reactive materials that are used as building blocks during assembly.…”

Section: Introductionmentioning

confidence: 99%

Covalently Crosslinked and Physically Stable Polymer Coatings with Chemically Labile and Dynamic Surface Features Fabricated by Treatment of Azlactone-Containing Multilayers with Alcohol-, Thiol-, and Hydrazine-Based Nucleophiles

Carter

Lynn

2016

Chem. Mater.

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We report approaches to the design of covalently crosslinked and physically stable surface coatings with chemically labile and dynamic surface features based on the functionalization of azlactone-containing materials with alcohol-, thiol-, and hydrazine-based nucleophiles. Past studies demonstrate that residual azlactone groups in polymer multilayers fabricated by the reactive layer-by-layer assembly of poly(2-vinyl-4,4-dimethylazlactone) and branched poly(ethylenimine) can react with amine-based nucleophiles to impart new surface and bulk properties through the creation of chemically stable amide/amide-type bonds. Here, we demonstrate that the azlactone groups in these covalently crosslinked materials can also be functionalized using less nucleophilic alcohol-or thiol-containing compounds, using an organic catalyst, or converted to reactive acylhydrazine groups by direct treatment with hydrazine. These methods (i) broaden the pool of molecules that can be used for post-fabrication functionalization to include compounds containing alcohol, thiol, or aldehyde groups, and (ii) yield surface coatings with chemically labile amide/ester-, amide/thioester-, and amide/iminetype bonds that make possible the design of new dynamic and stimuli-responsive materials (e.g., surfaces that release covalently-bound molecules or undergo changes in extreme wetting behaviours in response to specific chemical stimuli). Our results expand the range of functionality that can be installed in, and thus the range of new functions that can be imparted to, azlactone-containing coatings beyond those that can be accessed using primary amine-based nucleophiles. The chemical approaches demonstrated here using model polymer-based reactive multilayer coatings are general, and should thus also prove useful for the design of new responsive surfaces based on other types of azlactone-functionalized materials.

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Superhydrophobic polymer multilayers for the filtration‐ and absorption‐based separation of oil/water mixtures

Kratochvil

Manna

Lynn

2017

J. Polym. Sci. Part A: Polym. Chem.

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We report layer-by-layer approaches to the design of superhydrophobic and superoleophilic substrates for the filtration-or absorption-based separation of bulk oil from oil/ water mixtures. Fabrication of covalently cross-linked, nanoporous polymer multilayers on mesh substrates yielded superhydrophobic and superoleophilic porous media that allow oil to pass, but completely prevent the passage of bulk water. This approach can be used to promote the filtration of oil/water mixtures, and these film-coated substrates can be bent and physically manipulated without affecting oil-and water-wetting properties. Fabrication on three-dimensional macroporous polymer pads yielded flexible objects that float on water and absorb oil at contaminated air/water interfaces. This approach permits oil to be recovered by squeezing or rinsing with solvent and the reuse of these materials without decreases in performance. These pads can also absorb oil from simulated seawater, brine, and other media representative of marine or industrial contexts where oil contamination can occur. Our results address issues associated with the design of polymerbased coatings for the separation, removal, and collection of oil from oil-contaminated water. With further development, this approach could provide low-energy alternatives to conventional remediation methods or yield new strategies that can be implemented in ways that are impractical using current technologies.

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Covalent Layer‐by‐Layer Assembly Using Reactive Polymers

Cited by 11 publications

References 153 publications

Layer-by-Layer Assembly of Amine-Reactive Multilayers Using an Azlactone-Functionalized Polymer and Small-Molecule Diamine Linkers

Layer-by-Layer Assembly of Amine-Reactive Multilayers Using an Azlactone-Functionalized Polymer and Small-Molecule Diamine Linkers

Covalently Crosslinked and Physically Stable Polymer Coatings with Chemically Labile and Dynamic Surface Features Fabricated by Treatment of Azlactone-Containing Multilayers with Alcohol-, Thiol-, and Hydrazine-Based Nucleophiles

Superhydrophobic polymer multilayers for the filtration‐ and absorption‐based separation of oil/water mixtures

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