Al3+ Modification of Graphene Oxide Membranes: Effect of Al Source.

Graphene oxide (GO) membranes are promising materials for water filtration applications due to abundant nanochannels in the membrane structure. Because GO membranes are unstable in water, metal cations such as Al3+ are often introduced to the membrane structure to promote cross-linking between individual GO sheets. Here, we describe a simple yet versatile method to incorporate Al3+ into GO membranes formed via a slow self-assembly process. Specifically, we directly added aluminum to acidic GO sheet solutions from a variety of sources: Al2O3, AlCl3 and Al foil. Each species reacts differently with water, which can affect the GO solution pH and thus the density of carboxylate groups on the sheet edges available for cross-linking to the Al3+ cations. We demonstrate through characterization of the GO sheet solutions as well as the as-formed membranes' morphologies, hydrophobicities, and structures that the extent to which the Al3+ cross-links to the GO sheet edges vs. the GO sheet basal planes is dependent on the Al source. Our results indicate that greatest enhancements in the membrane stability occur when electrostatic and coordination interactions between Al3+ and the carboxylate groups on the GO sheet edges are more extensive than Al3+-π interactions between basal planes.

Tuning the Packing Density of Gold Nanoparticles in Peptoid Nanosheets Prepared at the Oil-Water Interface.

Two-dimensional (2D) arrays of gold nanoparticles that can freely float in water are promising materials for solution-based plasmonic applications like sensing. To be effective sensors, it is critical to control the interparticle gap distance and thus the plasmonic properties of the 2D arrays. Here, we demonstrate excellent control over the interparticle gap distance in a family of freely floating gold nanoparticle-embedded peptoid nanosheets. Nanosheets are made via monolayer assembly and collapse at the oil-water interface, allowing for fine control over the solution nanoparticle concentration during assembly. We used surface pressure measurements to monitor the assembly of the peptoid, nanoparticle, and combined system at the oil-water interface to determine a workable range of nanosheet assembly conditions suitable for controlling the interparticle gap distances within the nanosheets. These measurements revealed that the extent of nanoparticle adsorption to the peptoid monolayer can be tuned by varying the bulk nanoparticle concentration, but the ability for the monolayer to collapse into nanosheets is compromised at high nanoparticle concentrations. Peptoid nanosheets were synthesized with varying bulk nanoparticle concentrations and analyzed using light microscopy and UV-visible spectroscopy. Based on the spectral shift of the localized surface plasmon resonance peaks for the nanoparticles in the nanosheets relative to those well dispersed in toluene, we estimate that we can access interparticle gap distances within the nanosheet interior between 2.9 ± 0.5 and 9 ± 2 nm. Our results suggest that the minimum interparticle distance achievable by this method is limited by the nanoparticle ligand length, and so has the potential to be further tuned by varying the ligand chemical structure. The ability to quantitatively control and monitor the assembly conditions by this method provide an opportunity to readily tune the optoelectronic properties of this new class of 2D nanomaterial, making it a promising platform for plasmonic-based sensing applications.

Using Al3+ to Tailor Graphene Oxide Nanochannels: Impact on Membrane Stability and Permeability.

Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used in separation and filtration applications. This study employed a simple yet effective method of introducing trivalent aluminum cations to a GO sheet solution through the oxidation of aluminum foil, which modifies the nanochannels in the self-assembled GO membrane by increasing the inter-sheet distance while decreasing intra-sheet spacing. The Al3+ modification resulted in an increase in membrane stability in water, methanol, ethanol, and propanol, yet decreased membrane permeability to water and propanol. These changes were attributed to strong interactions between Al3+ and the membrane oxygenated functional groups, which resulted in an increase in membrane hydrophobicity and a decrease in the intra-sheet spacing as supported by surface tension, contact angle, atomic force microscopy, and X-ray photoelectron spectroscopy measurements. Our approach for forming Al3+ modified GO membranes provides a method for improving the aqueous stability and tailoring the permeation selectivity of GO membranes, which have the potential to be implemented in vapor separation and fuel purification applications.

Synthesis and characterization of plasmonic peptoid nanosheets.

Solvated two-dimensional (2D) arrays of gold nanoparticles (AuNPs) are versatile plasmonic materials that are not limited by the constraints of a solid support. We report here the assembly of AuNP-embedded peptoid nanosheets via monolayer collapse at the liquid-liquid interface. This synthesis route produces a new class of solvated 2D plasmonic arrays and has the potential to be extended to a variety of different nanoparticle systems.

Glycosylated Peptoid Nanosheets as a Multivalent Scaffold for Protein Recognition.

Glycoproteins adhered on the cellular membrane play a pivotal role in a wide range of cellular functions. Their importance is particularly relevant in the recognition process between infectious pathogens (such as viruses, bacteria, toxins) and their host cells. Multivalent interactions at the pathogen-cell interfaces govern binding events and can result in a strong and specific interaction. Here we report an approach to mimic the cell surface presentation of carbohydrate ligands by the multivalent display of sugars on the surface of peptoid nanosheets. The constructs provide a highly organized 2D platform for recognition of carbohydrate-binding proteins. The sugars were displayed using different linker lengths or within loops containing 2-6 hydrophilic peptoid monomers. Both the linkers and the loops contained one alkyne-bearing monomer, to which different saccharides were attached by copper-catalyzed azide-alkyne cycloaddition reactions. Peptoid nanosheets functionalized with different saccharide groups were able to selectively bind multivalent lectins, Concanavalin A and Wheat Germ Agglutinin, as observed by fluorescence microscopy and a homogeneous Förster resonance energy transfer (FRET)-based binding assay. To evaluate the potential of this system as sensor for threat agents, the ability of functionalized peptoid nanosheets to bind Shiga toxin was also studied. Peptoid nanosheets were functionalized with globotriose, the natural ligand of Shiga toxin, and the effective binding of the nanomaterial was verified by the FRET-based binding assay. In all cases, evidence for multivalent binding was observed by systematic variation of the ligand display density on the nanosheet surface. These cell surface mimetic nanomaterials may find utility in the inactivation of pathogens or as selective molecular recognition elements.

Structure-Rheology Relationship in Nanosheet-Forming Peptoid Monolayers.

Peptoid nanosheets are novel protein-mimetic materials that form from the supramolecular assembly of sequence-defined peptoid polymers. The component polymer chains organize themselves via a unique mechanism at the air-water interface, in which the collapse of a compressed peptoid monolayer results in free-floating, bilayer nanosheets. To impart functionality into these bilayer materials, structural engineering of the nanosheet-forming peptoid strand is necessary. We previously synthesized a series of peptoid analogues with modifications to the hydrophobic core in order to probe the nanosheet tolerance to different packing interactions. Although many substitutions were well-tolerated, routine surface pressure measurements and monolayer collapse isotherms were insufficient to explain which molecular processes contributed to the ability or inability of these peptoid analogues to form nanosheets. Here, we show that surface dilational rheology measurements of assembled peptoid monolayers at the air-water interface provide great insight into their nanosheet-forming ability. We find that a key property required for nanosheet formation is the ability to assemble into a solidlike monolayer in which the residence time of the peptoid within the monolayer is very long and does not exchange rapidly with the subphase. These collapse-competent monolayers typically have a characteristic time of diffusion-exchange values, τD, of >5000 s. Thus, rheological measurements provide an efficient method for assessing the nanosheet-forming ability of peptoid analogues. Results from these studies can be used to guide the rational design of peptoids for assembly into functional nanosheets.

Molecular Engineering of the Peptoid Nanosheet Hydrophobic Core.

The relationship between the structure of sequence-defined peptoid polymers and their ability to assemble into well-defined nanostructures is important to the creation of new bioinspired platforms with sophisticated functionality. Here, the hydrophobic N-(2-phenylethyl)glycine (Npe) monomers of the standard nanosheet-forming peptoid sequence were modified in an effort to (1) produce nanosheets from relatively short peptoids, (2) inhibit the aggregation of peptoids in bulk solution, (3) increase nanosheet stability by promoting packing interactions within the hydrophobic core, and (4) produce nanosheets with a nonaromatic hydrophobic core. Fluorescence and optical microscopy of individual nanosheets reveal that certain modifications to the hydrophobic core were well tolerated, whereas others resulted in instability or aggregation or prevented assembly. Importantly, we demonstrate that substitution at the meta and para positions of the Npe aromatic ring are well tolerated, enabling significant opportunities to tune the functional properties of peptoid nanosheets. We also found that N-aryl glycine monomers inhibit nanosheet formation, whereas branched aliphatic monomers have the ability to form nanosheets. An analysis of the crystal structures of several N,N'-disubstituted diketopiperazines (DKPs), a simple model system, revealed that the preferred solid-state packing arrangement of the hydrophobic groups can directly inform the assembly of stable peptoid nanosheets.

Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids.

An ability to develop sequence-defined synthetic polymers that both mimic lipid amphiphilicity for self-assembly of highly stable membrane-mimetic 2D nanomaterials and exhibit protein-like functionality would revolutionize the development of biomimetic membranes. Here we report the assembly of lipid-like peptoids into highly stable, crystalline, free-standing and self-repairing membrane-mimetic 2D nanomaterials through a facile crystallization process. Both experimental and molecular dynamics simulation results show that peptoids assemble into membranes through an anisotropic formation process. We further demonstrated the use of peptoid membranes as a robust platform to incorporate and pattern functional objects through large side-chain diversity and/or co-crystallization approaches. Similar to lipid membranes, peptoid membranes exhibit changes in thickness upon exposure to external stimuli; they can coat surfaces in single layers and self-repair. We anticipate that this new class of membrane-mimetic 2D nanomaterials will provide a robust matrix for development of biomimetic membranes tailored to specific applications.

Improved chemical and mechanical stability of peptoid nanosheets by photo-crosslinking the hydrophobic core.

Peptoid nanosheets can be broadly functionalized for a variety of applications. However, they are susceptible to degradation when exposed to chemical or mechanical stress. To improve their strength, photolabile monomers were introduced in order to crosslink the nanosheet interior. Photo-crosslinking produced a more robust material that can survive sonication, lyophilization, and other biochemical manipulations.

Design, Synthesis, Assembly, and Engineering of Peptoid Nanosheets.

Two-dimensional (2D) atomically defined organic nanomaterials are an important material class with broad applications. However, few general synthetic methods exist to produce such materials in high yields and to precisely functionalize them. One strategy to form ordered 2D organic nanomaterials is through the supramolecular assembly of sequence-defined synthetic polymers. Peptoids, one such class of polymer, are designable bioinspired heteropolymers whose main-chain length and monomer sequence can be precisely controlled. We have recently discovered that individual peptoid polymers with a simple sequence of alternating hydrophobic and ionic monomers can self-assemble into highly ordered, free-floating nanosheets. A detailed understanding of their molecular structure and supramolecular assembly dynamics provides a robust platform for the discovery of new classes of nanosheets with tunable properties and novel applications. In this Account, we discuss the discovery, characterization, assembly, molecular modeling, and functionalization of peptoid nanosheets. The fundamental properties of peptoid nanosheets, their mechanism of formation, and their application as robust scaffolds for molecular recognition and as templates for the growth of inorganic minerals have been probed by an arsenal of experimental characterization techniques (e.g., scanning probe, electron, and optical microscopy, X-ray diffraction, surface-selective vibrational spectroscopy, and surface tensiometry) and computational techniques (coarse-grained and atomistic modeling). Peptoid nanosheets are supramolecular assemblies of 16-42-mer chains that form molecular bilayers. They span tens of microns in lateral dimensions and freely float in water. Their component chains are highly ordered, with chains nearly fully extended and packed parallel to one another as a result of hydrophobic and electrostatic interactions. Nanosheets form via a novel interface-catalyzed monolayer collapse mechanism. Peptoid chains first assemble into a monolayer at either an air-water or oil-water interface, on which peptoid chains extend, order, and pack into a brick-like pattern. Upon mechanical compression of the interface, the monolayer buckles into stable bilayer structures. Recent work has focused on the design of nanosheets with tunable properties and functionality. They are readily engineerable, as functional monomers can be readily incorporated onto the nanosheet surface or into the interior. For example, functional hydrophilic "loops" have been displayed on the surfaces of nanosheets. These loops can interact with specific protein targets, serving as a potentially general platform for molecular recognition. Nanosheets can also bind metal ions and serve as 2D templates for mineral growth. Through our understanding of the formation mechanism, along with predicted features ascertained from molecular modeling, we aim to further design and synthesize nanosheets as robust protein mimetics with the potential for unprecedented functionality and stability.

Peptoid nanosheets exhibit a new secondary-structure motif.

A promising route to the synthesis of protein-mimetic materials that are capable of complex functions, such as molecular recognition and catalysis, is provided by sequence-defined peptoid polymers--structural relatives of biologically occurring polypeptides. Peptoids, which are relatively non-toxic and resistant to degradation, can fold into defined structures through a combination of sequence-dependent interactions. However, the range of possible structures that are accessible to peptoids and other biological mimetics is unknown, and our ability to design protein-like architectures from these polymer classes is limited. Here we use molecular-dynamics simulations, together with scattering and microscopy data, to determine the atomic-resolution structure of the recently discovered peptoid nanosheet, an ordered supramolecular assembly that extends macroscopically in only two dimensions. Our simulations show that nanosheets are structurally and dynamically heterogeneous, can be formed only from peptoids of certain lengths, and are potentially porous to water and ions. Moreover, their formation is enabled by the peptoids' adoption of a secondary structure that is not seen in the natural world. This structure, a zigzag pattern that we call a Σ('sigma')-strand, results from the ability of adjacent backbone monomers to adopt opposed rotational states, thereby allowing the backbone to remain linear and untwisted. Linear backbones tiled in a brick-like way form an extended two-dimensional nanostructure, the Σ-sheet. The binary rotational-state motif of the Σ-strand is not seen in regular protein structures, which are usually built from one type of rotational state. We also show that the concept of building regular structures from multiple rotational states can be generalized beyond the peptoid nanosheet system.

Twist and turn: effect of stereoconfiguration on the interfacial assembly of polyelectrolytes.

Understanding the conditions that promote the adsorption, assembly, and accumulation of charged macromolecules at the interface between aqueous and hydrophobic liquids is important to a multitude of biological, environmental, and industrial processes. Here, the oil-water interfacial behavior of stereoisomers of polymethacrylic acid (PMA), a model system for both naturally occurring and synthetic polyelectrolytes, is investigated with a combination of vibrational sum-frequency (VSF) spectroscopy, surface tension, and computations. Syndiotactic and isotactic isomers both show rapid adsorption to the oil-water interface with a net orientation indicative of a high degree of ordering. The stereoconfiguration is found to affect whether only a single layer or multiple layers assemble at the interface. Surface tension measurements show additional adsorption for syndiotactic PMA over time. The additional layers do not contribute to the VSF spectrum indicating disorder in all but the initial layer. The isotactic isomer shows no evidence of accumulation at the interface beyond the single ordered layer. Molecular dynamics calculations show marked differences between the two isomers in the orientation of their substituent groups at the interface. The hydrophilic and hydrophobic moieties in the isotactic isomer are easily partitioned to the water and oil phases, respectively, whereas a fair portion of hydrophobic groups remain in the water phase for the syndiotactic PMA. The available hydrophobic contacts in the water phase at the interface are credited with allowing further adsorption.

Assembly and molecular order of two-dimensional peptoid nanosheets through the oil-water interface.

Peptoid nanosheets are a recently discovered class of 2D nanomaterial that form from the self-assembly of a sequence-specific peptoid polymer at an air-water interface. Nanosheet formation occurs first through the assembly of a peptoid monolayer and subsequent compression into a bilayer structure. These bilayer materials span hundreds of micrometers in lateral dimensions and have the potential to be used in a variety of applications, such as in molecular sensors, artificial membranes, and as catalysts. This paper reports that the oil-water interface provides another opportunity for growth of these unique and highly ordered peptoid sheets. The monolayers formed at this interface are found through surface spectroscopic measurements to be highly ordered and electrostatic interactions between the charged moieties, namely carboxylate and ammonium residues, of the peptoid are essential in the ability of these peptoids to form ordered nanosheets at the oil-water interface. Expanding the mechanism of peptoid nanosheet formation to the oil-water interface and understanding the crucial role of electrostatic interactions between peptoid residues in nanosheet formation is essential for increasing the complexity and functionality of these nanomaterials.

Designated drivers: the differing roles of divalent metal ions in surfactant adsorption at the oil-water interface.

Divalent metal ions play numerous roles in biological, technological, and environmental systems. This study examines the role of a variety of ions, Mg(2+), Ca(2+), Mn(2+), Ni(2+), Cu(2+), and Zn(2+), in the adsorption of sodium decanoate at the carbon tetrachloride-water interface. For all ions studied, the ions drive the adsorption of the surfactant to the interface. Using vibrational sum-frequency spectroscopy and the carboxylic acid vibrational modes as a signature for metal ion binding, each metal salt is found to play a distinctly different role in the molecular characteristics of surfactant adsorption at the interface. Additional spectroscopic studies of the methyl and methylene vibrations are monitored to track the ordering of the alkyl chains when metal salts are added to solution. How the metal-surfactant binding impacts the surfactant structure, orientation, and solvation is explored. How these spectroscopic measurements compare with the degree of adsorption as measured by interfacial tension data is presented.

Chunks of charge: effects at play in the assembly of macromolecules at fluid surfaces.

Large macromolecules with hydrophobic backbones are known to assemble at the interface between immiscible liquids. This assembly is often unpredictable because of the subtle interplay among hydrophobic interactions, hydrophilic solvation, structural constraints, and the thermodynamics of adsorption. In these studies, we employ vibrational sum frequency spectroscopy and interfacial tension measurements to study the assembly of a simple polyelectrolyte, poly(methacrylic acid), as it assembles at the interface between two immiscible liquids, specifically, carbon tetrachloride and water. By adjusting the polyelectrolyte charge through pH studies and the polymer size through molecular weight studies, we demonstrate that charge accumulation in segments of the polymer chains is a critical factor in macromolecular interfacial adsorption and desorption. The results have implications for related charged macromolecules whose ability to assemble between two immiscible fluid media is essential for many biological processes, water remediation efforts, and enhanced oil recovery.

Metal ions: driving the orderly assembly of polyelectrolytes at a hydrophobic surface.

The accumulation of polyelectrolytes at the interface between water and nonpolar fluids is an important process in both environmental and biological systems. For instance, polyelectrolytes such as humic acids are highly charged molecules that play a role in the remediation of water contaminated by oil, and the adsorption of other polyelectrolytes such as proteins and DNA to cellular surfaces is essential in biological processes. The properties of these naturally occurring polyelectrolytes are highly tunable and depend strongly on the binding of metal ions commonly found in environmental and biological systems. While the metal complexation behaviors of many polyelectrolytes and biomolecules are well characterized in bulk solution, this work shows in molecular detail that the behavior of a common polyelectrolyte in the presence of metal ions can be quite different when it adsorbs to a hydrophobic-aqueous liquid interface. In these studies, vibrational sum frequency spectroscopy and interfacial tension measurements conducted on poly(acrylic acid) (PAA) at a model oil-water interface show how small amounts of monovalent and divalent cations significantly alter the interfacial conformation of PAA at the interface and act to enhance its interfacial adsorption. The results provide important new insights that have direct relevance for understanding the effect of metal ions on the adsorption of charged macromolecules to a hydrophobic-aqueous boundary layer, specifically in biological and environmental systems.

Ordered polyelectrolyte assembly at the oil-water interface.

Polyelectrolytes (PEs) are widely used in applications such as water purification, wastewater treatment, and mineral recovery. Although much has been learned in past decades about the behavior of PEs in bulk aqueous solutions, their molecular behavior at a surface, and particularly an oil-water interface where many of their applications are most relevant, is largely unknown. From these surface spectroscopic and thermodynamics studies we report the unique molecular characteristics that several common polyelectrolytes, poly(acrylic acid) and poly(methylacrylic acid), exhibit when they adsorb at a fluid interface between water and a simple insoluble organic oil. These PEs are found to adsorb to the interface from aqueous solution in a multistepped process with a very thin initial layer of oriented polymer followed by multiple layers of randomly oriented polymer. This additional layering is thwarted when the PE conformation is constrained. The adsorption/desorption process is highly pH dependent and distinctly different than what might be expected from bulk aqueous phase behavior.

Unique assembly of charged polymers at the oil-water interface.

Understanding the interfacial adsorption of polymers has become increasingly important because a wide range of scientific disciplines utilize these macromolecular structures to facilitate processes such as nanoparticle assembly, environmental remediation, electrical multilayer assembly, and surfactant adsorption. Structure and adsorption characteristics for poly(acrylic acid) at the oil-water interface have been studied using vibrational sum frequency spectroscopy and interfacial tension to increase the comprehension of polyelectrolyte structure at interfaces. The adsorption of poly(acrylic acid) to the oil-water interface from the aqueous phase is found to be highly pH dependent and occurs in a multistep process, with the initial polymer adsorption displaying a high degree of conformational ordering.