Stiff Shape Memory Polymers for High-Resolution Reconfigurable Nanophotonics.

Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. Yet, a longstanding challenge is in overcoming stiction caused by van der Waals forces in the deformed configuration, which impedes shape recovery. Here, we introduce stiff shape memory polymers. This designer material has a storage modulus of ∼5.2 GPa at room temperature and ∼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of ∼400 nm and an aspect ratio as high as ∼10 were printed by two-photon lithography. Experimentally, we observe shape recovery as collapsed and touching structures overcome stiction to stand back up. We develop a theoretical model to explain the recoverability of these sub-micrometer structures. Reconfigurable structural color prints with a resolution of 21150 dots per inch and holograms are demonstrated, indicating potential applications of the stiff shape memory polymers in high-resolution reconfigurable nanophotonics.

Massively Multiplexed Submicron Particle Patterning in Acoustically Driven Oscillating Nanocavities.

Nanoacoustic fields are a promising method for particle actuation at the nanoscale, though THz frequencies are typically required to create nanoscale wavelengths. In this work, the generation of robust nanoscale force gradients is demonstrated using MHz driving frequencies via acoustic-structure interactions. A structured elastic layer at the interface between a microfluidic channel and a traveling surface acoustic wave (SAW) device results in submicron acoustic traps, each of which can trap individual submicron particles. The acoustically driven deformation of nanocavities gives rise to time-averaged acoustic fields which direct suspended particles toward, and trap them within, the nanocavities. The use of SAWs permits massively multiplexed particle manipulation with deterministic patterning at the single-particle level. In this work, 300 nm diameter particles are acoustically trapped in 500 nm diameter cavities using traveling SAWs with wavelengths in the range of 20-80 µm with one particle per cavity. On-demand generation of nanoscale acoustic force gradients has wide applications in nanoparticle manipulation, including bioparticle enrichment and enhanced catalytic reactions for industrial applications.

Physical Texturing for Superhydrophobic Polymeric Surfaces: A Design Perspective.

Surface wetting on the textured surface is classically explained by the theories of Cassie-Baxter or Wenzel. However, in recent years, an increasing number of complex surface topographies with superhydrophobic properties have been achieved without prediction or simulation using these theories. One example is biomimetic surfaces. In many instances, theories were used to explain surface properties found in nature but have not led to or predicted the complex topographies. Although new wetting theories continue to emerge, there is not yet a set of design rules to guide the selection of surface topographies to achieve superhydrophobicity. By grouping known surface topographies into common geometrical descriptions and length scale, this paper suggests a set of surface topography classifications to provide selection guidelines for engineering superhydrophobic surfaces. Two key outcomes emerged from the design analysis: first, categorization of frequently reported surface patterns shows that there exists a set of commonly used descriptions among diverse designs; second, the degree of hydrophobicity improvement within a class of topography design can be used to predict the limit of improvement in superhydrophobicity for a given material. The presentation of topography descriptors by categories of design and performance may serve as a prologue to an eventually complete set of design guidelines for superhydrophobic performance.

Geometry-dependent compressive responses in nanoimprinted submicron-structured shape memory polyurethane.

High resolution surface textures, when rationally designed, provide an attractive surface engineering approach to enhance surface functionalities. Designing smart surfaces by coupling surface texture with shape memory polymers has garnered attention in achieving tunable mechanical properties. We investigate the structure-mechanical property relationships for programmable, shape-memorizing submicron-scale pillar arrays subjected to flat-punch compression. The geometrically-dependent deformation of structured surfaces with two different aspect ratios (250 nm-pillars 1 : 1 and 550 nm-pillars 2.4 : 1) were investigated, and their moduli were found to be lower than that of non-patterned surface. From finite element analysis, the pillar deformation is correlated to a mechanistic transition from a discrete, unidirectional compression of 250 nm-pillars to lateral constraints caused by interpillar contact in 550 nm-pillars. This lateral pillar-pillar contact in the 550 nm-pillars resulted in an increased and maximum strain-dependent modulus but lower elastic recovery and energy dissipation as compared with the 250 nm-pillars. Furthermore, the compressive responses of temporarily shaped pillars (programmed by stretching) were compared with the permanently shaped pillars. The extent of lateral constraints controlled by pillar shape and spacing in 550 nm-pillars was responsible for the modulus differences between the original and stretched patterns, whereas the modulus of 250 nm-pillars remained as a constant value with different levels of stretching. This study provides mechanistic insights into how the mechanical behavior can be modulated by designing the aspect ratio of shape memory pillar arrays and by programming the surface geometry, thus revealing the potential of developing ingenious designs of responsive surfaces sensitive to mechanical deformation.

Bioinspired ultrahigh water pinning nanostructures.

Rose petal mimetic surfaces with ultrahigh water pinning forces have been fabricated via nanoimprinting process onto three different polymer films. Water pinning forces ranging from 104 to 690 µN are obtained on free-standing polycarbonate films with imprinted nanostructures. Through a systematic variation of the surface structures, this study provides experimental evidence that an ultrahigh water pinning force can be achieved by combining two surface topographical designs: (1) conical- or parabolic-shaped nanoprotrusions and (2) isotropic and continuous nanoprotrusions. These design criteria ensure that a continuous solid-liquid contact line is achieved and provide a rule-of-thumb to engineer surfaces with tunable water pinning forces. The ultrahigh water pinning film is further demonstrated to mitigate the "coffee ring" effect, a phenomenon associated with nonuniform deposition from a drying solute-laden liquid droplet.

Substrate topography determines the fate of chondrogenesis from human mesenchymal stem cells resulting in specific cartilage phenotype formation.

To reproduce a complex and functional tissue, it is crucial to provide a biomimetic cellular microenvironment that not only incorporates biochemical cues, but also physical features including the nano-topographical patterning, for cell/matrix interaction. We developed spatially-controlled nano-topography in the form of nano-pillar, nano-hole and nano-grill on polycaprolactone surface via thermal nanoimprinting. The effects of chondroitin sulfate-coated nano-topographies on cell characteristics and chondrogenic differentiation of human mesenchymal stem cell (MSC) were investigated. Our results show that various nano-topographical patterns triggered changes in MSC morphology and cytoskeletal structure, affecting cell aggregation and differentiation. Compared to non-patterned surface, nano-pillar and nano-hole topography enhanced MSC chondrogenesis and facilitated hyaline cartilage formation. MSCs experienced delayed chondrogenesis on nano-grill topography and were induced to fibro/superficial zone cartilage formation. This study demonstrates the sensitivity of MSC differentiation to surface nano-topography and highlights the importance of incorporating topographical design in scaffolds for cartilage tissue engineering. From the clinical editor: These authors have developed spatially-controlled nano-topography in the form of nano-pillar, nano-hole and nano-grill on polycaprolactone surface via thermal nanoimprinting, and the effects of chondroitin sulfate-coated nano-topographies on cell characteristics and chondrogenic differentiation of human mesenchymal stem cells (MSC) were investigated. It has been concluded that MSC differentiation is sensitive to surface nano-topography, and certain nano-imprinted surfaces are more useful than others for cartilage tissue engineering.

Early integrin binding to Arg-Gly-Asp peptide activates actin polymerization and contractile movement that stimulates outward translocation.

Integrin-mediated adhesions are critical for stem cell differentiation, cancer metastasis, and the immune response [Hynes RO (2009) Science 326:1216-1219]. However, the mechanisms of early adhesion formation remain unclear, especially the effects of lateral clustering of integrins and the role of the Src family kinases. Using mobile Arg-Gly-Asp (RGD) peptide ligands on lipid bilayers with nano-fabricated physical barriers [Salaita K, et al. (2010) Science 327:1380-1385], we observe surprising long-range lateral movements of ligated integrins during the process of cell spreading. Initially, RGD-activated integrin clusters stimulate actin polymerization that radiates from the clusters. Myosin II contraction of actin from adjacent clusters produces contractile pairs that move toward each other against barriers. Force generated by myosin II stimulates a Src kinase-dependent lamellipodial extension and outward movement of clusters. Subsequent retraction by myosin II causes inward movement of clusters. The final cell spread area increases with the density of periodic barriers. Early integrin clustering recruits adhesion proteins, talin, paxillin, and FAK, irrespective of force generation. However, recruitment of vinculin is only observed upon contraction. Thus, we suggest that integrin activation and early clustering are independent of lateral forces. Clustering activates Src-dependent actin polymerization from clusters. Myosin contraction of clusters to lines stimulates active spreading with outward forces from actin polymerization followed by a second wave of contraction. Many of these early mechanical steps are not evident in cells spreading on immobilized matrices perhaps because of the low forces involved. These observations can provide new targets to control integrin-dependent adhesion and motility.

Reversible recovery of nanoimprinted polymer structures.

A shape memory polymer, Nafion, has its shape memory simultaneously programmed and patterned with micro- and nanometer-scale surface textures using a nanoimprint process. Highly ordered and well-defined micro- and nanometer surface textures, for example, high aspect ratio (~5) micropillars, form the permanent shape memory of the Nafion films. When damaged, these permanently shaped micro- and nanostructures possess repair ability through a heat treatment. Reversible recoveries of the damages caused by mechanical and irradiation exposure have been demonstrated. The recovery retains above 90% of the structural fidelity, which is comparable to the shape recovery in bulk film.

Individually addressable patterned multilayer microchambers for site-specific release-on-demand.

Patterned arrays of light-responsive microchambers are suggested as candidates for site-specific release of chemicals in small and precisely defined quantities on demand. A composite film is made of poly(allylammonium)-poly(styrene sulfonate) multilayers and gold nanoparticles incorporated between subsequent stacks of polyelectrolytes. The film shaped as microchambers is loaded with colloid particles or oil-soluble molecules. The microchambers are sealed onto a glass slide precoated with an adhesive poly(diallyldimethylammonium)-poly(styrene sulfonate) multilayer film. A focused laser beam is used for remote addressing the individual microchambers and site-specific release of the loaded cargo.

Triple and Quadruple Surface Pattern Memories in Nanoimprinted Polymer Blends.

Trigger-responsive surfaces with multiple surface properties have wide-ranging application potential from surfaces with trigger-responsive fluid flow to cell culture to optical effects; such surfaces can be achieved through surface morphological changes. Although multiple shape-memory effects are successful in bulk polymers, there is limited programing and recovery of multiple surface memories due to the challenges in fabricating multiple surface topographies with good controllability. Here, we report the synergy between the polymer blend formulation and the thermal nanoimprinting process to achieve multiple microtopography memories. A series of immiscible blends consisting of poly(caprolactone) (PCL) and polyethylene (PE) with distinct thermal transitions governed by distinct crystallization events were augmented with improved elasticity through preferential cross-linking in the polymer blend. The effect of preferential cross-linking by dicumyl peroxide on the elastic property of the PCL/PE has been found to be nonlinearly dependent on the blend composition. This approach enabled triple and quadruple surface pattern fixity and recovery in nanoimprinted PCL/PE blends. Specifically, we demonstrated the recovery of a micropillar structure (diameter: 20 µm and height: 10 µm) from a hierarchical micrograting topography (width: 2 µm and height: 2 µm) when exposed to a thermal stimulus at 60 °C for 180 s. Furthermore, we also demonstrated the recovery of a deformed micrograting followed by a secondary recovery of the micropillar structure.

All Knitted and Integrated Soft Wearable of High Stretchability and Sensitivity for Continuous Monitoring of Human Joint Motion.

E-textiles have recently gained significant traction in the development of soft wearables for healthcare applications. However, there have been limited works on wearable e-textiles with embedded stretchable circuits. Here, stretchable conductive knits with tuneable macroscopic electrical and mechanical properties are developed by varying the yarn combination and the arrangement of stitch types at the meso-scale. Highly extensible piezoresistive strain sensors are designed (>120% strain) with high sensitivity (gauge factor 8.47) and durability (>100,000 cycles), interconnects (>140% strain) and resistors (>250% strain), optimally arranged to form a highly stretchable sensing circuit. The wearable is knitted with a computer numerical control (CNC) knitting machine that offers a cost effective and scalable fabrication method with minimal post-processing. The real-time data from the wearable is transmitted wirelessly using a custom designed circuit board. In this work, an all knitted and fully integrated soft wearable is demonstrated for wireless and continuous real-time sensing of knee joint motion of multiple subjects performing various activities of daily living.

Design and Performance Evaluation of a Fully Integrated Knitted Knee Brace for Knee Motion Sensing.

The use of e-textiles in wearable sensor design has recently received much interest in many applications, such as robotics, rehabilitation, personal wellness, and sports. Particularly in the rehabilitation domain, it has provided a potential alternative tool for telerehabilitation. In this paper, we designed and evaluated a knitted knee brace with interconnects, resistors, and sensors for real-time kinematic data acquisition. The real-time data acquisition is transmitted using a printed circuit board (PCB) connected to the knee brace through snap pins. The knitted knee brace was tested on three male and one female participant , aged between 30 and 50 years old. All participants were instructed to perform a walking activity at 1.5 km/h for a duration of 10 seconds on the Advanced Mechanical Technology, Inc (AMTI) treadmill over two sessions. The results demonstrated that the fully integrated knitted wearable knee brace could monitor and track human joint locomotion in real time with a standard deviation of 0.39V and 0.41V , respectively, for these two sessions. However, double peak signals were noticeable from the knitted knee brace at a mean of 80.54% during the gait cycles across the four subjects; this observation could be due to the coupled motion along the transverse and coronal planes during the activity.

Microarray with micro- and nano-topographies enables identification of the optimal topography for directing the differentiation of primary murine neural progenitor cells.

During development and tissue repair, progenitor cells are guided by both biochemical and biophysical cues of their microenvironment, including topographical signals. The topographical cues have been shown to play an important role in controlling the fate of cells. Systematic investigation of topographical structures with different geometries and sizes under the identical experimental conditions on the same chip will enhance the understanding of the role of shape and size in cell-topography interactions. A simple customizable multi-architecture chip (MARC) array is therefore developed to incorporate, on a single chip, distinct topographies of various architectural complexities, including both isotropic and anisotropic features, in nano- to micrometer dimensions, with different aspect ratios and hierarchical structures. Polydimethylsiloxane (PDMS) replicas of MARC are used to investigate the influence of different geometries and sizes in neural differentiation of primary murine neural progenitor cells (mNPCs). Anisotropic gratings (2 µm gratings, 250 nm gratings) and isotropic 1 µm pillars significantly promote differentiation of mNPCs into neurons, as indicated by expression of ß-III-tubulin (59%, 58%, and 58%, respectively, compared to 30% on the control). In contrast, glial differentiation is enhanced on isotropic 2 µm holes and 1 µm pillars. These results illustrate that anisotropic topographies enhance neuronal differentiation while isotropic topographies enhance glial differentiation on the same chip under the same conditions. MARC enables simultaneous cost-effective investigation of multiple topographies, allowing efficient optimization of topographical and biochemical cues to modulate cell differentiation.

Adhesion of polyelectrolyte multilayers: sealing and transfer of microchamber arrays.

Polyelectrolyte multilayer (PEM) films with array of responsive microchambers are promising candidates for site-specific release of chemicals in small and precisely defined quantities on demand. It requires effective sealing of the microchambers toward a support to prevent leakage of a cargo. In this paper, we study the pressure-induced adhesion of poly(allylammonium)-poly(4-styrenesulfonate) (PAH-PSS) multilayers assembled on different templates toward the poly(4-styrenesulfonate)-poly(diallyldimethylammonium) multilayer. The tensile bond strength increases from 0.4 to 3.5 MPa upon the increase of PAH-PSS bilayers from 10 to 40, if assembled on a silicon template. Weaker tensile bond strength of 0.35 MPa between the PAH-PSS multilayer and a poly(methylmethacrylate) (PMMA) template results in adhesive break at this interface and allows mechanical removal of the template. The successful PEM transfer is demonstrated for templates of various geometrical patterns, while the tensile break of a multilayer film happens for the others.

High resolution UV roll-to-roll nanoimprinting of resin moulds and subsequent replication via thermal nanoimprint lithography.

UV roll-to-roll nanoimprinting at high resolution is still a relatively unexplored field of study with far-reaching application potential. One enabling technology that is particularly worthy of attention is mass production of high resolution resin moulds via UV roll-to-roll nanoimprinting at such high throughput and low cost that they can be used only once and disposed of or recycled economically. Low cost, high resolution resin moulds can greatly improve the production cost profile for a number of applications in biomedicine, nanofluidics, data storage and electronics with relatively low unit values but which require one or more nanoscale lithography steps. In this report, UV roll-to-roll nanoimprinting was employed to fabricate high fidelity resin moulds with nanoscale as well as mixed micro- and nanoscale features down to 50 nm feature diameter, at up to 120 cm(2) area and at 10 m min(-1) throughput. UV roll-to-roll nanoimprinted resin moulds were subsequently segmented out, employed in a batch mode thermal nanoimprinting process, and characterized to study performance and demonstrate viability. The results show that high resolution mixed nanostructures can be faithfully replicated in PMMA on silicon substrates with minimal volumetric shrinkage. Process details and challenges specific to roll-to-roll fabrication of resin moulds are discussed at length, particularly with respect to the curvature uniformity of the imprint roller.

Direct nanoimprint lithography of Al2O3 using a chelated monomer-based precursor.

Nanostructuring of Al2O3 is predominantly achieved by the anodization of aluminum film and is limited to obtaining porous anodized aluminum oxide (AAO). One of the main restrictions in developing approaches for direct fabrication of various types of Al2O3 patterns, such as lines, pillars, holes, etc, is the lack of a processable aluminum-containing resist. In this paper, we demonstrate a stable precursor prepared by reacting aluminum tri-sec-butoxide with 2-(methacryloyloxy)ethyl acetoacetate, a chelating monomer, which can be used for large area direct nanoimprint lithography of Al2O3. Chelation in the precursor makes it stable against hydrolysis whilst the presence of a reactive methacrylate group renders it polymerizable. The precursor was mixed with a cross-linker and their in situ thermal free-radical co-polymerization during nanoimprinting rigidly shaped the patterns, trapped the metal atoms, reduced the surface energy and strengthened the structures, thereby giving a ~100% yield after demolding. The imprinted structures were heat-treated, leading to the loss of organics and their subsequent shrinkage. Amorphous Al2O3 patterns with line-widths as small as 17 nm were obtained. Our process utilizes the advantages of sol-gel and methacrylate routes for imprinting and at the same time alleviates the disadvantages associated with both these methods. With these benefits, the chelating monomer route may be the harbinger of the universal scheme for direct nanoimprinting of metal oxides.

Peculiarities of polyelectrolyte multilayer assembly on patterned surfaces.

The layer-by-layer assembly of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate) is studied on templates with imprinted arrays of microwells ranging from 2 to 25 µm and different aspect ratios. The thickness and microstructure of polyelectrolyte multilayers (PEMs) are measured using scanning electron microscopy. At 0.2 M ionic strength, the PEM film evenly coats the template both inside and outside the microwells. If the film is thinner than the critical value of about 400 nm, PEM microstructures collapse upon dissolving the template. Euler's model of critical stress is used to describe the collapse. At 2 M ionic strength, a substantially thinner PEM film is assembled inside the 25 µm wells than outside. If the well diameter is reduced to 7 and 2 µm, a much thicker PEM film is formed inside the microwells. These observations have been attributed to the changing of polyelectrolyte conformation in the solutions.

Enhanced ordering in gold nanoparticles self-assembly through excess free ligands.

Self-assembly of nanometer-sized particles is an elegant and economical approach to achieve dense patterns over large areas beyond the resolution and throughput capabilities of electron-beam lithography. In this paper, we present results of self-assembly of oleylamine-capped gold nanoparticles with 8.0 ± 0.3 nm diameter into densely packed and well-ordered monolayers with center-to-center distance of ∼11 nm. Self-assembly was done in a Langmuir-Blodgett trough and picked up onto Si substrates. The nanoparticles undesirably assembled within micrometer-sized "droplets" that were organic in nature. However, within these droplets, we observed that the addition of the excess ligand, oleylamine, drastically enhanced the self-assembly of the nanoparticles into monolayers with near-perfect ordering. This approach has the potential use in templated self-assembly of nanoparticles for rearranging poorly ordered assembly into a commensurate prepatterned substrate.

Phototriggerable Transient Electronics via Fullerene-Mediated Degradation of Polymer:Fullerene Encapsulation Layer.

Transient electronics is an emerging class of electronics that has attracted a lot of attention because of its potential as an environmental-friendly alternative to the existing end-of-life product disposal or treatments. However, the controlled degradation of transient electronics under environmentally benign conditions remains a challenge. In this work, the tunable degradation of transient electronics including passive resistor devices and active memory devices was realized by photodegradable thin polymer films comprising fullerene derivatives, [6,6]-phenyl-C61-butyric acid methyl esters (PCBM). The photodegradation of polymer:PCBM under an aqueous environment is triggered by ultraviolet (UV) light. Experimental results demonstrate that the addition of PCBM in commodity polymers, including but not limited to polystyrene, results in a catalytic effect on polymer photodegradation when triggered by UV light. The degradation mechanism of transient electronics is ascribed to the photodegradation of polymer:PCBM encapsulation layers caused by the synergistic effect between UV and water exposure. The polymer:PCBM encapsulation system presented herein offers a simple way to achieve the realization of light-triggered device degradation for bioapplication and expands the material options for tailorable degradation of transient electronics.

Superhydrophobic Polymer Topography Design Assisted by Machine Learning Algorithms.

Superhydrophobic surfaces have been largely achieved through various surface topographies. Both empirical and numerical simulations have been reported to help understand and design superhydrophobic surfaces. Many such successful surfaces have also been achieved using bioinspired and biomimetic designs. Despite this, identifying the right surface texture to meet the requirements of specific applications is not a straightforward task. Here, we report a hybrid approach that includes experimental methods, numerical simulations, and machine learning (ML) algorithms to create design maps for superhydrophobic polymer topographies. Two design objectives to investigate superhydrophobic properties were the maximum water contact angle (WCA) and Laplace pressure. The design parameters were the geometries of an isotropic pillar structure in micrometer and sub-micrometer length scales. The finite element method (FEM) was validated by the experimental data and employed to generate a labeled dataset for ML training. Artificial neural network (ANN) models were then trained on the labeled database for the topographic parameters (width W, height H, and pitch P) with the corresponding WCA and Laplace pressure. The ANN models yielded a series of nonlinear relationships between the topographic design parameters and the WCA and Laplace pressure and substantial differences between the micrometer and sub-micrometer length scales. Design maps that span the topography design parameters provide optimal design or tradeoff parameters. This research demonstrates the potential of ANN as a rapid design tool for surface topography exploration.