Nanomotor-enhanced transport of passive Brownian particles in porous media.

Artificial micro/nanomotors are expected to perform tasks in interface-rich and species-rich environments for biomedical and environmental applications. In these highly confined and interconnected pore spaces, active species may influence the motion of coexisting passive participants in unexpected ways. Using three-dimensional super-resolution single-nanoparticle tracking, we observed enhanced motion of passive nanoparticles due to the presence of dilute well-separated nanomotors in an interconnected pore space. This enhancement acted at distances that are large compared to the sizes of the particles and cavities, in contrast with the insignificant effect on the passive particles with the same dilute concentration of nanomotors in an unconfined liquid. Experiments and simulations suggested an amplification of hydrodynamic coupling between self-propelled and passive nanoparticles in the interconnected confined environment, which enhanced the effective energy for passive particles to escape cavities through small holes. This finding represents an emergent behavior of confined nanomotors and suggests new strategies for the development of antifouling membranes and drug delivery systems.

Designing Interfacial Reactions for Nanometer-Scale Surface Patterning of PDMS with Controlled Elastic Modulus.

Control over the surface chemistry of elastomers such as polydimethylsiloxane (PDMS) is important for many applications. However, achieving nanostructured chemical control on amorphous material interfaces below the length scale of substrate heterogeneity is not straightforward, and can be particularly difficult to decouple from changes in network structure that are required for certain applications (e.g., variation of elastic modulus for cell culture). We have recently reported a new method for precisely structured surface functionalization of PDMS and other soft materials, which displays high densities of ligands directly on the material surface, maximizing steric accessibility. Here, we systematically examine structural factors in the PDMS components (e.g., base and cross-linker structures) that impact efficiency of the interfacial reaction that leads to surface functionalization. Applying this understanding, we demonstrate routes for generating equivalent nanometer-scale functional patterns on PDMS with elastic moduli from 0.013 to 1.4 MPa, establishing a foundation for use in applications such as cell culture.

Surface-Templated Glycopolymer Nanopatterns Transferred to Hydrogels for Designed Multivalent Carbohydrate-Lectin Interactions across Length Scales.

Multivalent interactions between carbohydrates and proteins enable a broad range of selective chemical processes of critical biological importance. Such interactions can extend from the macromolecular scale (1-10 nm) up to much larger scales across a cell or tissue, placing substantial demands on chemically patterned materials aiming to leverage similar interactions in vitro. Here, we show that diyne amphiphiles with carbohydrate headgroups can be assembled on highly oriented pyrolytic graphite (HOPG) to generate nanometer-resolution carbohydrate patterns, with individual linear carbohydrate assemblies up to nearly 1 µm, and microscale geometric patterns. These are then photopolymerized and covalently transferred to the surfaces of hydrogels. This strategy suspends carbohydrate patterns on a relatively rigid polydiacetylene (persistence length ∼ 16 nm), exposed at the top surface of the hydrogel above the bulk pore structure. Transferred patterns of appropriate carbohydrates (e.g., N-acetyl-d-glucosamine, GlcNAc) enable selective, multivalent interactions (KD ∼ 40 nM) with wheat germ agglutinin (WGA), a model lectin that exhibits multivalent binding with appropriately spaced GlcNAc moieties. WGA binding affinity can be further improved (KD ∼ 10 nM) using diacetylenes that shift the polymer backbone closer to the displayed carbohydrate, suggesting that this strategy can be used to modulate carbohydrate presentation at interfaces. Conversely, GlcNAc-patterned surfaces do not induce specific binding of concanavalin A, and surfaces patterned with glucuronic acid, or with simple carboxylic acid or hydroxyl groups, do not induce WGA binding. More broadly, this approach may have utility in designing synthetic glycan-mimetic interfaces with features from molecular to mesoscopic scales, including soft scaffolds for cells.

Nanometer-scale patterning of hard and soft interfaces: from photolithography to molecular-scale design.

Many areas of modern materials chemistry, from nanoscale electronics to regenerative medicine, require design of precisely-controlled chemical environments at near-molecular scales. Most work on high-resolution interface patterning to date has focused on hard surfaces, such as those for electronics. However, design of interfaces for biological environments increasingly requires precise control over interfaces of soft materials, which is in many cases complicated by nano-to-microscale heterogeneity in the substrate material. In this Feature Article, we describe historical approaches to nanoscale patterning on hard surfaces, challenges in extension to soft interfaces, and an approach to molecular-scale hard and soft interface design based on self-assembled molecular networks, which can be assembled noncovalently on hard surfaces to generate nanometer-scale patterns, then covalently transferred to soft materials including PDMS and hydrogels.

Nanostructured Surface Functionalization of Polyacrylamide Hydrogels Below the Length Scale of Hydrogel Heterogeneity.

Hydrogels are broadly used in applications where polymer materials must interface with biology. The hydrogel network is amorphous, with substantial heterogeneity on length scales up to hundreds of nanometers, in some cases raising challenges for applications that would benefit from highly structured interactions with biomolecules. Here, we show that it is possible to generate ordered patterns of functional groups on polyacrylamide hydrogel surfaces. We demonstrate that, when linear patterns of amines are transferred to polyacrylamide, they pattern interactions with DNA at the interface, a capability of potential importance for preconcentration in chromatographic applications, as well as for the development of nanostructured hybrid materials and supports for cell culture.

Nanometer-Scale Precision Polymer Patterning of PDMS: Multiscale Insights into Patterning Efficiency Using Alkyldiynamines.

Most high-resolution interfacial patterning approaches are restricted to crystalline inorganic interfaces. Recently, we have shown that it is possible to generate 1 nm resolution functional patterns on soft materials, such as polydimethylsiloxane (PDMS), by creating highly structured striped patterns of functional alkyldiacetylenes on a hard crystalline surface, photopolymerizing to set the molecular pattern as a striped-phase polydiacetylene (sPDA), and then covalently transferring the sPDAs to PDMS. Transfer depends on the diacetylene polymerization, making it important to understand design principles for efficient sPDA polymerization and cross-linking to PDMS. Here, we combine single-molecule and fluorescence-based metrics for sPDA polymerization and transfer, first to characterize sPDA polymerization of amine striped phases, and then to develop a probabilistic model that describes the transfer process in terms of sPDA-PDMS cross-linking reaction efficiency and number of reactions required for transfer. We illustrate that transferred patterns of alkylamines can be used to direct both adsorption of CdSe nanocrystals with alkyl ligand shells and covalent reactions with fluorescent dyes, highlighting the utility of functional patterning of the PDMS surface.

Lipids: An Atomic Toolkit for the Endless Frontier.

The evolution of lipids in nanoscience exemplifies the powerful coupling of advances in science and technology. Here, we describe two waves of discovery and innovation in lipid materials: one historical and one still building. The first wave leveraged the relatively simple capability for lipids to orient at interfaces, building layers of functional groups. This simple form of building with atoms yielded a stunning range of technologies: lubricant additives that dramatically extended machine lifetimes, molecules that enabled selective ore extraction in mining, and soaps that improved human health. It also set the stage for many areas of modern nanoscience. The second wave of lipid materials, still growing, uses the more complex toolkits lipids offer for building with atoms, including controlling atomic environment to control function (e.g., pKa tuning) and the generation of more arbitrary two-dimensional and three-dimensional structures, including lipid nanoparticles for COVID-19 mRNA vaccines.

Plenty of Room at the Top: A Multi-Scale Understanding of nm-Resolution Polymer Patterning on 2D Materials.

Lamellar phases of alkyldiacetylenes in which the alkyl chains lie parallel to the substrate represent a straightforward means for scalable 1-nm-resolution interfacial patterning. This capability has the potential for substantial impacts in nanoscale electronics, energy conversion, and biomaterials design. Polymerization is required to set the 1-nm functional patterns embedded in the monolayer, making it important to understand structure-function relationships for these on-surface reactions. Polymerization can be observed for certain monomers at the single-polymer scale using scanning probe microscopy. However, substantial restrictions on the systems that can be effectively characterized have limited utility. Here, using a new multi-scale approach, we identify a large, previously unreported difference in polymerization efficiency between the two most widely used commercial diynoic acids. We further identify a core design principle for maximizing polymerization efficiency in these on-surface reactions, generating a new monomer that also exhibits enhanced polymerization efficiency.

Oleylamine Impurities Regulate Temperature-Dependent Hierarchical Assembly of Ultranarrow Gold Nanowires on Biotemplated Interfaces.

Nanocrystals are often synthesized using technical grade reagents such as oleylamine (OLAm), which contains a blend of 9-cis-octadeceneamine with trans-unsaturated and saturated amines. Here, we show that gold nanowires (AuNWs) synthesized with OLAm ligands undergo thermal transitions in interfacial assembly (ribbon vs. nematic); transition temperatures vary widely with the batch of OLAm used for synthesis. Mass spectra reveal that higher-temperature AuNW assembly transitions are correlated with an increased abundance of trans and saturated chains in certain blends. DSC thermograms show that both pure (synthesized) and technical-grade OLAm have primary melting transitions near -5 °C (20-30 °C lower than the literature melting temperature range of OLAm). A second, broader melting transition (in the previous reported melting range) appears in technical grade blends; its temperature varies with the abundance of trans and saturated chains. Our findings illustrate that, similar to biological membranes, blends of alkyl chains can be used to generate mesoscopic hierarchical nanocrystal assembly, particularly at interfaces that further modulate transition temperatures.

One Nanometer Wide Functional Patterns with a Sub-10 Nanometer Pitch Transferred to an Amorphous Elastomeric Material.

Decades of work in surface science have established the ability to functionalize clean inorganic surfaces with sub-nm precision, but for many applications, it would be useful to provide similar control over the surface chemistry of amorphous materials such as elastomers. Here, we show that striped monolayers of diyne amphiphiles, assembled on graphite and photopolymerized, can be covalently transferred to polydimethylsiloxane (PDMS), an elastomer common in applications including microfluidics, soft robotics, wearable electronics, and cell culture. This process creates precision polymer films <1 nm thick, with 1 nm wide functional patterns, which control interfacial wetting and reactivity, and template adsorption of flexible, ultranarrow Au nanowires. The polydiacetylenes exhibit polarized fluorescence emission, revealing polymer location, orientation, and environment, and resist engulfment, a common problem in PDMS functionalization. These findings illustrate a route for patterning surface chemistry below the length scale of heterogeneity in an amorphous material.

Large-Scale Noncovalent Functionalization of 2D Materials through Thermally Controlled Rotary Langmuir-Schaefer Conversion.

As two-dimensional (2D) materials are more broadly utilized as components of hybrid materials, controlling their surface chemistry over large areas through noncovalent functionalization becomes increasingly important. Here, we demonstrate a thermally controlled rotary transfer stage that allows areas of a 2D material to be continuously cycled into contact with a Langmuir film. This approach enables functionalization of large areas of the 2D material and simultaneously improves long-range ordering, achieving ordered domain areas up to nearly 10 000 µm2. To highlight the layer-by-layer processing capability of the rotary transfer stage, large-area noncovalently adsorbed monolayer films from an initial rotary cycle were used as templates to assemble ultranarrow gold nanowires from solution. The process we demonstrate would be readily extensible to roll-to-roll processing, addressing a longstanding challenge in scaling Langmuir-Schaefer transfer for practical applications.

Combination of single-molecule magnet behaviour and luminescence properties in a new series of lanthanide complexes with tris(pyrazolyl)borate and oligo(ß-diketonate) ligands.

A series of tris(pyrazolyl)borate mono-, di- and trinuclear complexes, [Tp2Ln]nX (Ln = Eu, Tb, Gd, Dy, Xn- = various mono-, bis- and tris(ß-diketonates) has been prepared. The Tb3+ and Dy3+ complexes are luminescent single molecular magnets (SMM) and exhibit luminescence quantum efficiencies up to 73% for the Tb3+ and 4.4% for the Dy3+ compounds. Similar Eu3+ complexes display bright emission only at lower temperatures. The Dy3+ and Tb3+ complexes possess SMM behavior in a non-zero dc field at low temperatures, while the polynuclear Dy3+ complexes also show slow magnetic relaxation even in zero dc field up to 8 K. Ueff-values determined from dynamic magnetic measurements were up to 31 and 6 cm-1 for the Dy3+ and Tb3+ complexes, respectively. It was found that within a series of Dy3+ and Tb3+ compounds, Ueff and luminescence quantum yields decreased with increasing nuclearity of the compounds and a shortening of the intramolecular Ln-Ln distance. ΔOrbach-values estimated from low-temperature luminescence spectra were significantly higher than those obtained from ac magnetic data, which may be due to involvement of additional processes in the relaxation mechanism (quantum tunneling, Raman, direct) reducing the energy barrier. Some of the Tb3+-compounds also display metal-centred electroluminescence, giving them potential as emitting layers in LEDs.