Interplay of the forces governing steroid hormone micropollutant adsorption in vertically-aligned carbon nanotube membrane nanopores.

Vertically-aligned carbon nanotube (VaCNT) membranes allow water to conduct rapidly at low pressures and open up the possibility for water purification and desalination, although the ultralow viscous stress in hydrophobic and low-tortuosity nanopores prevents surface interactions with contaminants. In this experimental investigation, steroid hormone micropollutant adsorption by VaCNT membranes is quantified and explained via the interplay of the hydrodynamic drag and friction forces acting on the hormone, and the adhesive and repulsive forces between the hormone and the inner carbon nanotube wall. It is concluded that a drag force above 2.2 × 10-3 pN overcomes the friction force resulting in insignificant adsorption, whereas lowering the drag force from 2.2 × 10-3 to 4.3 × 10-4 pN increases the adsorbed mass of hormones from zero to 0.4 ng cm-2. At a low drag force of 1.6 × 10-3 pN, the adsorbed mass of four hormones is correlated with the hormone-wall adhesive (van der Waals) force. These findings explain micropollutant adsorption in nanopores via the forces acting on the micropollutant along and perpendicular to the flow, which can be exploited for selectivity.

Ion and Hydrodynamic Translucency in 1D van der Waals Heterostructured Boron-Nitride Single-Walled Carbon Nanotubes.

An unresolved challenge in nanofluidics is tuning ion selectivity and hydrodynamic transport in pores, particularly for those with diameters larger than a nanometer. In contrast to conventional strategies that focus on changing surface functionalization or confinement degree by varying the radial dimension of the pores, we explore a unique approach for manipulating ion selectivity and hydrodynamic flow enhancement by externally coating single-walled carbon nanotubes (SWCNTs) with a few layers of hexagonal boron nitride (h-BN). For van der Waals heterostructured BN-SWCNTs, we observed a 9-fold increase in cation selectivity for K+ versus Cl- compared to pristine SWCNTs of the same 2.2 nm diameter, while hydrodynamic slip lengths decreased by more than an order of magnitude. These results suggest that the single-layer graphene inner surface may be translucent to charge-regulation and hydrodynamic-slip effects arising from h-BN on the outside of the SWCNT. Such 1D heterostructures could serve as synthetic platforms with tunable properties for exploring distinct nanofluidic phenomena and their potential applications.

Growth and Performance of High-Quality SWCNT Forests on Inconel Foils as Lithium-Ion Battery Anodes.

Large-scale production of vertically aligned single-walled carbon nanotubes (VA-SWCNTs) on metal foils promises to enable technological advancements in many fields, from functional composites to energy storage to thermal interfaces. In this work, we demonstrate growth of high-quality (G/D > 6, average diameters ∼ 2-3 nm, densities > 1012 cm-2) VA-SWCNTs on Inconel metal for use as a lithium-ion battery (LIB) anode. Scale-up of SWCNT growth on Inconel 625 to 100 cm2 exhibits nearly invariant CNT structural properties, even when synthesis is performed near atmospheric pressure, and this robustness is attributed to a growth kinetic regime dominated by the carbon precursor diffusion in the bulk gas mixture. SWCNT forests produced on large-area metal substrates at close to atmospheric pressure possess a combination of structural features that are among the best demonstrated so far in the literature for growth on metal foils. Leveraging these achievements for energy applications, we demonstrate a VA-SWCNT LIB anode with capacity >1200 mAh/g at 1.0C and stable cycling beyond 300 cycles. This robust synthesis of high-quality VA-SWCNTs on metal foils presents a promising route toward mass production of high-performance CNT devices for a broad range of applications.

On-Demand Dynamic Chirality Selection in Flower Corolla-like Micropillar Arrays.

Chiral morphology has been intensively studied in various fields including biology, organic chemistry, pharmaceuticals, and optics. On-demand and dynamic chiral inversion not only cannot be realized in most intrinsically chiral materials but also has mostly been limited to chemical or light-induced methods. Herein, we report reversible real-time magneto-mechanical chiral inversion of a three-dimensional (3D) micropillar array between achiral, clockwise, and counterclockwise chiral arrangements. Inspired by the flower corolla, achiral arrays of five and six radially arranged semicylindrical micropillars were employed as model systems to investigate the dynamic symmetry properties of arrays consisting of odd and even numbers of micropillars, respectively. Each micropillar underwent twisting actuation with a different twisting angle depending on the angle with the magnetic field direction and magnetic flux density, thereby collectively changing the chirality from the achiral to chiral state. Importantly, the morphological handedness of the micropillars was inverted within a few seconds by manipulating the direction of the magnetic field. A chiral morphology consisting of magnetically twisted micropillars was shape-fixed by the introduction of a polymeric binder. This binder could be simply washed off to return the shape-fixed twisted micropillars to their initial straight state. Magnetically programmable and reproducible 3D flower corolla-like micropillar arrays are expected to expand the potential of shape-reconfigurable devices that require real-time chiral manipulation in ambient environments.

Programmable Stepwise Collective Magnetic Self-Assembly of Micropillar Arrays.

Chain-like magnetic self-organizations have been documented for micron/submicron-scale magnetic particles. However, the positions of the particles are not stationary in a sustaining fluid owing to Brownian translational motion, resulting in irregular magnetic self-assembly. Toward the development of a programmable and reversible magnetic self-assembly, we report a stepwise collective magnetic self-assembly with periodic polymeric micropillar arrays containing magnetic particles. Under an external magnetic field, the individual micropillar acts as a micromagnet; magnetic polarities of embedded ferromagnetic particles are arranged in the same direction. The nearest pillar tops undergo a pairwise assembly owing to the anisotropic quadrupolar interaction, whereas the pillar bases remain stationary because of the presence of a magnetically inert substrate. By increasing the magnetic flux density, a collective quad-body assembly of vicinal paired micropillars is accomplished, finally leading to long-range connectivity of the pillar tops. Simple evaporation of the polymeric solution yields shape-fixation of the connected micropillar architectures even after magnetic fields are removed. We investigate geometric effects on this stepwise collective magnetic self-assembly using rectangular, square, and circular micropillars. Also, we demonstrate spatially selective magnetic self-assembly (e.g., arbitrary letters) using a masking technique. Finally, we demonstrate on-demand programming of bidirectional liquid spreading through long-range ordered magnetic self-assembly.

Fast Permeation of Small Ions in Carbon Nanotubes.

Simulations and experiments have revealed enormous transport rates through carbon nanotube (CNT) channels when a pressure gradient drives fluid flow, but comparatively little attention has been given to concentration-driven transport despite its importance in many fields. Here, membranes are fabricated with a known number of single-walled CNTs as fluid transport pathways to precisely quantify the diffusive flow through CNTs. Contrary to early experimental studies that assumed bulk or hindered diffusion, measurements in this work indicate that the permeability of small ions through single-walled CNT channels is more than an order of magnitude higher than through the bulk. This flow enhancement scales with the ion free energy of transfer from bulk solutions to a nanoconfined, lower-dielectric environment. Reported results suggest that CNT membranes can unlock dialysis processes with unprecedented efficiency.

Ultra-Permeable Single-Walled Carbon Nanotube Membranes with Exceptional Performance at Scale.

Enhanced fluid transport in single-walled carbon nanotubes (SWCNTs) promises to enable major advancements in many membrane applications, from efficient water purification to next-generation protective garments. Practical realization of these advancements is hampered by the challenges of fabricating large-area, defect-free membranes containing a high density of open, small diameter SWCNT pores. Here, large-scale (≈60 cm2) nanocomposite membranes comprising of an ultrahigh density (1.89 × 1012 tubes cm-2) of 1.7 nm SWCNTs as sole transport pathways are demonstrated. Complete opening of all conducting nanotubes in the composite enables unprecedented accuracy in quantifying the enhancement of pressure-driven transport for both gases (>290× Knudsen prediction) and liquids (6100× no-slip Hagen-Poiseuille prediction). Achieved water permeances (>200 L m-2 h-1 bar-1) greatly exceed those of state-of-the-art commercial nano- and ultrafiltration membranes of similar pore size. Fabricated membranes reject nanometer-sized molecules, permit fractionation of dyes from concentrated salt solutions, and exhibit excellent chemical resistance. Altogether, these SWCNT membranes offer new opportunities for energy-efficient nano- and ultrafiltration processes in chemically demanding environments.

Enhancement of Magneto-Mechanical Actuation of Micropillar Arrays by Anisotropic Stress Distribution.

Magnetically active shape-reconfigurable microarrays undergo programmed actuation according to the arrangement of magnetic dipoles within the structures, achieving complex twisting and bending deformations. Cylindrical micropillars have been widely used to date, whose circular cross-sections lead to identical actuation regardless of the actuating direction. In this study, micropillars with triangular or rectangular cross-sections are designed and fabricated to introduce preferential actuation directions and explore the limits of their actuation. Using such structures, controlled liquid wetting is demonstrated on micropillar surfaces. Liquid droplets pinned on magnetic micropillar arrays undergo directional spreading when the pillars are actuated as depinning of the droplets is enabled only in certain directions. The enhanced deformation due to direction dependent magneto-mechanical actuation suggests that micropillar arrays can be fundamentally tailored to possess application specific responses and opens up opportunities to exploit more complex designs such as micropillars with polygonal cross sections. Such tunable wetting of liquids on microarray surfaces has potential to improve printing technologies via contactless reconfiguration of stamp geometry by magnetic field manipulation.

Strong, Ultralight Nanofoams with Extreme Recovery and Dissipation by Manipulation of Internal Adhesive Contacts.

Advances in three-dimensional nanofabrication techniques have enabled the development of lightweight solids, such as hollow nanolattices, having record values of specific stiffness and strength, albeit at low production throughput. At the length scales of the structural elements of these solids-which are often tens of nanometers or smaller-forces required for elastic deformation can be comparable to adhesive forces, rendering the possibility to tailor bulk mechanical properties based on the relative balance of these forces. Herein, we study this interplay via the mechanics of ultralight ceramic-coated carbon nanotube (CNT) structures. We show that ceramic-CNT foams surpass other architected nanomaterials in density-normalized strength and that, when the structures are designed to minimize internal adhesive interactions between CNTs, more than 97% of the strain after compression beyond densification is recovered. Via experiments and modeling, we study the dependence of the recovery and dissipation on the coating thickness, demonstrate that internal adhesive contacts impede recovery, and identify design guidelines for ultralight materials to have maximum recovery. The combination of high recovery and dissipation in ceramic-CNT foams may be useful in structural damping and shock absorption, and the general principles could be broadly applied to both architected and stochastic nanofoams.

Shape-Programmed Fabrication and Actuation of Magnetically Active Micropost Arrays.

Micro- and nanotextured surfaces with reconfigurable textures can enable advancements in the control of wetting and heat transfer, directed assembly of complex materials, and reconfigurable optics, among many applications. However, reliable and programmable directional shape in large scale is significant for prescribed applications. Herein, we demonstrate the self-directed fabrication and actuation of large-area elastomer micropillar arrays, using magnetic fields to both program a shape-directed actuation response and rapidly and reversibly actuate the arrays. Specifically, alignment of magnetic microparticles during casting of micropost arrays with hemicylindrical shapes imparts a deterministic anisotropy that can be exploited to achieve the prescribed, large-deformation bending or twisting of the pillars. The actuation coincides with the finite element method, and we demonstrate reversible, noncontact magnetic actuation of arrays of tens of thousands of pillars over hundreds of cycles, with the bending and twisting angles of up to 72 and 61°, respectively. Moreover, we demonstrate the use of the surfaces to control anisotropic liquid spreading and show that the capillary self-assembly of actuated micropost arrays enables highly complex architectures to be fabricated. The present technique could be scaled to indefinite areas using cost-effective materials and casting techniques, and the principle of shape-directed pillar actuation can be applied to other active material systems.

Synthetic Butterfly Scale Surfaces with Compliance-Tailored Anisotropic Drop Adhesion.

Many natural surfaces such as butterfly wings, beetles' backs, and rice leaves exhibit anisotropic liquid adhesion; this is of fundamental interest and is important to applications including self-cleaning surfaces, microfluidics, and phase change energy conversion. Researchers have sought to mimic the anisotropic adhesion of butterfly wings using rigid surface textures, though natural butterfly scales are sufficiently compliant to be deflected by capillary forces exerted by drops. Here, inspired by the flexible scales of the Morpho aega butterfly wing, synthetic surfaces coated with flexible carbon nanotube (CNT) microscales with anisotropic drop adhesion properties are fabricated. The curved CNT scales are fabricated by a strain-engineered chemical vapor deposition technique, giving ≈5000 scales of ≈10 µm thickness in a 1 cm2 area. Using various designed CNT scale arrays, it is demonstrated that the anisotropy of drop roll-off angle is influenced by the geometry, compliance, and hydrophobicity of the scales; and a maximum roll-off anisotropy of 6.2° is achieved. These findings are supported by a model that relates the adhesion anisotropy to the scale geometry, compliance, and wettability. The electrical conductivity and mechanical robustness of the CNTs, and the ability to fabricate complex multidirectional patterns, suggest further opportunities to create engineered synthetic scale surfaces.

Mycobacterium tuberculosis Controls Phagosomal Acidification by Targeting CISH-Mediated Signaling.

Pathogens have evolved a range of mechanisms to counteract host defenses, notably to survive harsh acidic conditions in phagosomes. In the case of Mycobacterium tuberculosis, it has been shown that regulation of phagosome acidification could be achieved by interfering with the retention of the V-ATPase complexes at the vacuole. Here, we present evidence that M. tuberculosis resorts to yet another strategy to control phagosomal acidification, interfering with host suppressor of cytokine signaling (SOCS) protein functions. More precisely, we show that infection of macrophages with M. tuberculosis leads to granulocyte-macrophage colony-stimulating factor (GM-CSF) secretion, inducing STAT5-mediated expression of cytokine-inducible SH2-containing protein (CISH), which selectively targets the V-ATPase catalytic subunit A for ubiquitination and degradation by the proteasome. Consistently, we show that inhibition of CISH expression leads to reduced replication of M. tuberculosis in macrophages. Our findings further broaden the molecular understanding of mechanisms deployed by bacteria to survive.

Predictive Synthesis of Freeform Carbon Nanotube Microarchitectures by Strain-Engineered Chemical Vapor Deposition.

High-throughput fabrication of microstructured surfaces with multi-directional, re-entrant, or otherwise curved features is becoming increasingly important for applications such as phase change heat transfer, adhesive gripping, and control of electromagnetic waves. Toward this goal, curved microstructures of aligned carbon nanotubes (CNTs) can be fabricated by engineered variation of the CNT growth rate within each microstructure, for example by patterning of the CNT growth catalyst partially upon a layer which retards the CNT growth rate. This study develops a finite-element simulation framework for predictive synthesis of complex CNT microarchitectures by this strain-engineered growth process. The simulation is informed by parametric measurements of the CNT growth kinetics, and the anisotropic mechanical properties of the CNTs, and predicts the shape of CNT microstructures with impressive fidelity. Moreover, the simulation calculates the internal stress distribution that results from extreme deformation of the CNT structures during growth, and shows that delamination of the interface between the differentially growing segments occurs at a critical shear stress. Guided by these insights, experiments are performed to study the time- and geometry-depended stress development, and it is demonstrated that corrugating the interface between the segments of each microstructure mitigates the interface failure. This study presents a methodology for 3D microstructure design based on "pixels" that prescribe directionality to the resulting microstructure, and show that this framework enables the predictive synthesis of more complex architectures including twisted and truss-like forms.

Simultaneously high stiffness and damping in nanoengineered microtruss composites.

Materials combining high stiffness and mechanical energy dissipation are needed in automotive, aviation, construction, and other technologies where structural elements are exposed to dynamic loads. In this paper we demonstrate that a judicious combination of carbon nanotube engineered trusses held in a dissipative polymer can lead to a composite material that simultaneously exhibits both high stiffness and damping. Indeed, the combination of stiffness and damping that is reported is quite high in any single monolithic material. Carbon nanotube (CNT) microstructures grown in a novel 3D truss topology form the backbone of these nanocomposites. The CNT trusses are coated by ceramics and by a nanostructured polymer film assembled using the layer-by-layer technique. The crevices of the trusses are then filled with soft polyurethane. Each constituent of the composite is accurately modeled, and these models are used to guide the manufacturing process, in particular the choice of the backbone topology and the optimization of the mechanical properties of the constituent materials. The resulting composite exhibits much higher stiffness (80 times) and similar damping (specific damping capacity of 0.8) compared to the polymer. Our work is a step forward in implementing the concept of materials by design across multiple length scales.

Measurement of carbon nanotube microstructure relative density by optical attenuation and observation of size-dependent variations.

Engineering the density of carbon nanotube (CNT) forest microstructures is vital to applications such as electrical interconnects, micro-contact probes, and thermal interface materials. For CNT forests on centimeter-scale substrates, weight and volume can be used to calculate density. However, this is not suitable for smaller samples, including individual microstructures, and moreover does not enable mapping of spatial density variations within the forest. We demonstrate that the relative mass density of individual CNT microstructures can be measured by optical attenuation, with spatial resolution equaling the size of the focused spot. For this, a custom optical setup was built to measure the transmission of a focused laser beam through CNT microstructures. The transmittance was correlated with the thickness of the CNT microstructures by Beer-Lambert-Bouguer law to calculate the attenuation coefficient. We reveal that the density of CNT microstructures grown by CVD can depend on their size, and that the overall density of arrays of microstructures is affected significantly by run-to-run process variations. Further, we use the technique to quantify the change in CNT microstructure density due to capillary densification. This is a useful and accessible metrology technique for CNTs in future microfabrication processes, and will enable direct correlation of density to important properties such as stiffness and electrical conductivity.

Statistical analysis of variation in laboratory growth of carbon nanotube forests and recommendations for improved consistency.

While many promising applications have been demonstrated for vertically aligned carbon nanotube (CNT) forests, lack of consistency in results (e.g., CNT quality, height, and density) continues to hinder knowledge transfer and commercialization. For example, it is well known that CNT growth can be influenced by small concentrations of water vapor, carbon deposits on the reactor wall, and experiment-to-experiment variations in pressure within the reaction chamber. However, even when these parameters are controlled during synthesis, we found that variations in ambient lab conditions can overwhelm attempts to perform parametric optimization studies. We established a standard growth procedure, including the chemical vapor deposition (CVD) recipe, while we varied other variables related to the furnace configuration and experimental procedure. Statistical analysis of 280 samples showed that ambient humidity, barometric pressure, and sample position in the CVD furnace contribute significantly to experiment-to-experiment variation. We investigated how these factors lead to CNT growth variation and recommend practices to improve process repeatability. Initial results using this approach reduced run-to-run variation in CNT forest height and density by more than 50%.

Genome-based cryptic gene discovery and functional identification of NRPS siderophore peptide in Streptomyces peucetius.

Identification of secondary metabolites produced by cryptic gene in bacteria may be difficult, but in the case of nonribosomal peptide (NRP)-type secondary metabolites, this study can be facilitated by bioinformatic analysis of the biosynthetic gene cluster and tandem mass spectrometry analysis. To illustrate this concept, we used mass spectrometry-guided bioinformatic analysis of genomic sequences to identify an NRP-type secondary metabolite from Streptomyces peucetius ATCC 27952. Five putative NRPS biosynthetic gene clusters were identified in the S. peucetius genome by DNA sequence analysis. Of these, the sp970 gene cluster encoded a complete NRPS domain structure, viz., C-A-T-C-A-T-E-C-A-T-C-A-T-C domains. Tandem mass spectrometry revealed that the functional siderophore peptide produced by this cluster had a molecular weight of 644.4 Da. Further analysis demonstrated that the siderophore peptide has a cyclic structure and an amino acid composition of AchfOrn-Arg-hOrn-hfOrn. The discovery of functional cryptic genes by analysis of the secretome, especially of NRP-type secondary metabolites, using mass spectrometry together with genome mining may contribute significantly to the development of pharmaceuticals such as hybrid antibiotics.

Fabrication, densification, and replica molding of 3D carbon nanotube microstructures.

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques (1, 2), and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization (3).

Engineering of micro- and nanostructured surfaces with anisotropic geometries and properties.

Widespread approaches to fabricate surfaces with robust micro- and nanostructured topographies have been stimulated by opportunities to enhance interface performance by combining physical and chemical effects. In particular, arrays of asymmetric surface features, such as arrays of grooves, inclined pillars, and helical protrusions, have been shown to impart unique anisotropy in properties including wetting, adhesion, thermal and/or electrical conductivity, optical activity, and capability to direct cell growth. These properties are of wide interest for applications including energy conversion, microelectronics, chemical and biological sensing, and bioengineering. However, fabrication of asymmetric surface features often pushes the limits of traditional etching and deposition techniques, making it challenging to produce the desired surfaces in a scalable and cost-effective manner. We review and classify approaches to fabricate arrays of asymmetric 2D and 3D surface features, in polymers, metals, and ceramics. Analytical and empirical relationships among geometries, materials, and surface properties are discussed, especially in the context of the applications mentioned above. Further, opportunities for new fabrication methods that combine lithography with principles of self-assembly are identified, aiming to establish design principles for fabrication of arbitrary 3D surface textures over large areas.

Corrugated carbon nanotube microstructures with geometrically tunable compliance.

Deterministic organization of nanostructures into microscale geometries is essential for the development of materials with novel mechanical, optical, and surface properties. We demonstrate scalable fabrication of 3D corrugated carbon nanotube (CNT) microstructures, via an iterative sequence of vertically aligned CNT growth and capillary self-assembly. Vertical microbellows and tilted microcantilevers are created over large areas, and these structures can have thin walls with aspect ratios exceeding 100:1. We show these structures can be used as out-of-plane microsprings with compliance determined by the wall thickness and number of folds.