Two-dimensional nanomaterials play a critical role in biology (e.g., lipid bilayers) and electronics (e.g., graphene) but are difficult to directly synthesize with a high level of precision. Peptoid nanosheet bilayers are a versatile synthetic platform for constructing multifunctional, precisely ordered two-dimensional nanostructures. Here we show that nanosheet formation occurs through an unusual monolayer intermediate at the air-water interface. Lateral compression of a self-assembled peptoid monolayer beyond a critical collapse pressure results in the irreversible production of nanosheets. An unusual thermodynamic cycle is employed on a preparative scale, where mechanical energy is used to buckle an intermediate monolayer into a more stable nanosheet. Detailed physical studies of the monolayer-compression mechanism revealed a simple preparative technique to produce nanosheets in 95% overall yield by cyclical monolayer compressions in a rotating closed vial. Compression of monolayers into stable, free-floating products may be a general and preparative approach to access 2D nanomaterials.
The ability of antibodies to bind a wide variety of analytes with high specificity and high affinity make them ideal candidates as molecular recognition elements for chemical and biological sensors. However, their widespread use in sensing devices has been hampered by their poor stability and high production cost. Here we report the design and synthesis of a new class of antibody-mimetic materials based on functionalized peptoid nanosheets. A high density of conformationally constrained peptide and peptoid loops are displayed on the surface of free-floating nanosheets to generate an extended, multivalent two-dimensional material that is chemically and biologically stable. The nanosheet serves as a robust, high-surface area scaffold upon which to display a wide variety of functional loop sequences. The functionalized nanosheets were characterized by atomic force microscopy, X-ray diffraction, and X-ray reflectivity measurements, and were shown to serve as substrates for enzymes (protease and casein kinase II), as well as templates for the growth of defined inorganic materials (gold metal).
Significance
Peptoid nanosheets are an emerging class of 2D nanomaterials that have the potential for use in a variety of applications ranging from molecular sensors to artificial enzymes. Because peptoids are highly designable polymers, nanosheets provide a general platform on which to display an enormous diversity of functionalities. Nanosheets are known to form through a unique monolayer compression mechanism, catalyzed by the air–water interface. Here we demonstrate that nanosheets can be formed via adsorption of peptoids at an oil–water interface. Using vibrational sum frequency spectroscopy, we show that electrostatic interactions are essential in the formation of an ordered peptoid monolayer at the interface, a critical intermediate in the nanosheet assembly pathway. These findings open the door for enhancing the complexity and functionality of 2D nanomaterials.
Organic two-dimensional nanomaterials are of growing importance, yet few general synthetic methods exist to produce them in high yields and to precisely functionalize them. We previously developed an efficient hierarchical supramolecular assembly route to peptoid bilayer nanosheets, where the organization of biomimetic polymer sequences is catalyzed by an air-water interface. Here we determine at which stages of assembly the nanoscale and atomic-scale order appear. We used X-ray scattering, grazing incidence X-ray scattering at the air-water interface, electron diffraction, and a recently developed computational coarse-grained peptoid model to probe the molecular ordering at various stages of assembly. We found that lateral packing and organization of the chains occurs during the formation of a peptoid monolayer, prior to its collapse into a bilayer. Identifying the structure-determining step enables strategies to influence nanosheet order, to predict and optimize production yields, and to further engineer this class of material. More generally, our results provide a guide for using fluid interfaces to catalytically assemble 2D nanomaterials.
The driving force for the adsorption of nanoparticles (5-10 nm) at the oil-water interface can be small and is particularly sensitive to the surface chemistry of the particles. Here we show that the interfacial assembly of 5 and 10 nm diameter gold nanoparticles functionalized with stoichiometric ion-pairs is reversible and can be tuned with the solution pH. We also show that at the interface the nanoparticles form a reflective layer with a mirror-like reflectance. Using titration we demonstrate that the mechanism for particle desorption from the interface is the electrostatic repulsion between the nanoparticles, likely due to pH-dependent adsorption of hydroxide ions. By controlling electrostatic repulsion we can control both the extent of adsorption at the interface and the separation between particles within the interfacial film. As such, we demonstrate two avenues to reversibly control the optical properties of the fluid interface: (1) increase the pH of the aqueous solution to desorb particles from the interface, and (2) decrease the ionic strength in the aqueous phase to increase the spacing of the nanoparticles at the oil-water interface.
We demonstrate that noncovalent ion-pair interactions in solution can be employed to control the molecular spacing of thiols in a self-assembled monolayer (SAM) on gold. Ion-pairs formed between the carboxylate tail-group of 16-mercaptohexadecanoic acid (MHA) and tetraalkylammonium (TAA+) hydroxide salts of various alkyl side-chain lengths remain intact during chemisorption of the thiol on gold. The resulting ion-pair SAMs exhibit a 1:1 molar ratio of MHA:TAA+ on the surface and are covalently bound to the gold surface through the thiol headgroup of MHA. We hypothesize that the incorporation of the bulky TAA+ group competes with the strong tendency of the thiols to organize into an ordered monolayer, which highlights the strength of the ion-pair complexes. The ion-pair films can be converted into a loosely packed MHA monolayer by rinsing the SAM with a solution of potassium perchlorate, which releases the TAA+ from the surface. Contact angle measurements and X-ray spectroscopy (XPS) confirm the stoichiometry and covalent attachment of the monolayers. XPS analysis and contact angle measurements indicate that the surface density of bound MHA decreases with increasing size of the TAA+ cation. These results suggest that steric hindrance created by the bulky side-chains of the TAA+ cation dictates the lateral spacing of MHA chains on the surface.
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