Mix and Match: Coassembly of Amphiphilic Dendrimers and Phospholipids Creates Robust, Modular, and Controllable Interfaces

Abstract

Self-assembly of supramolecular structures has become an attractive means to create new biologically inspired materials and interfaces. We report the first robust hybrid bilayer systems readily coassembled from amphiphilic dendrimers and a naturally occurring phospholipid. Both concentration and generation of the dendrimers have direct impacts on the biophysical properties of the coassemblies. Raising the dendrimer concentration increases the hybrid bilayer stability, while changes in the generation and the concentration of the embedded dendrimers impact the fluidity of the coassembled systems. Multivalent dendrimer amine terminals allow for nondestructive in situ derivatization, providing a convenient approach to decorate and modulate the local environment of the hybrid bilayer. The coassembly of lipid/dendrimer interfaces offers a unique platform for the creation of hybrid systems with modular and precisely controllable behavior for further applications in sensing and drug delivery.

Nanostructured Lipid‐Based Films for Substrate‐Mediated Applications in Biotechnology

“…Besides block copolymers, another type of synthetic polymer (dendrimer) was employed to form lipid-dendrimer co-assembly structures on solid supports. [145] The hybrid dendrimer/POPC vesicles were exposed to the hydrophilic substrates and incubated in an aqueous environment to allow them to form a well-defined supported bilayer. The fluidity and stability of the membrane could be modulated by controlling the generation (the number of repeated branching cycles) and concentration of the dendrimer.…”

Surface Plasmon Resonance: Material and Interface Design for Universal Accessibility

“…155,156 There are many ways to construct supported lipid bilayers, 156 including vesicle fusion over a hydrated surface 44,157 or attachment to an underlying surface chemistry, 158 which allows for surface-based analyses, such as SPR, to be conducted. 76,156 Cheng and co-workers developed a benchtop method for creating nanoscale layers of glass on gold SPR substrates via a layer-by-layer deposition and calcination (LbL/calcination) approach, which produced hydrophilic surfaces that were capable of promoting vesicle fusion toward a fluid supported lipid bilayer on an SPR chip. 159–161 These nanoglassified gold sensor surfaces were used in the analysis of membrane bound proteins by SPR 157 and SPRi, 162 with Hinman et al recently utilizing the methods to study the formation of hybrid bilayer interfaces consisting of phosphocholine and synthetic amphiphilic dendrimers.…”

“…159–161 These nanoglassified gold sensor surfaces were used in the analysis of membrane bound proteins by SPR 157 and SPRi, 162 with Hinman et al recently utilizing the methods to study the formation of hybrid bilayer interfaces consisting of phosphocholine and synthetic amphiphilic dendrimers. 76 Supported lipid bilayers on nanoglassified SPR chips have been extensively applied for the investigation of water-soluble deep cavitands, which self-incorporate into the bilayer, forming a pocket capable of hosting a wide variety of proteins and functionalized molecules. 114,163–165 Perez et al demonstrated the use of these cavitands embedded within a supported lipid membrane for site-specific polymer growth at this biomimetic interface, enabling the attachment of nonadherent cells and proteins.…”

Synthesis and Self‐Assembly of Stimuli‐Responsive Amphiphilic Dendrimers

“…The dendritic building blocks that are highly branched, compact, and globular are unlikely to form entanglements, allowing for facile control over morphologies compared to the linear block copolymers. [29,30] Moreover, multiple terminal groups of the dendrimers can be functionalized to control surface or interfacial properties and incorporate additional biological functionalities including targeting moieties. [27,31] Overall, amphiphilic dendrimers serve as attractive building blocks for the supramolecular construction of nanostructured materials with desirable properties.…”