A Sewing Approach to the Fabrication of Eco/bioresorbable Electronics.

Eco/bioresorbable electronics represent an emerging class of technology defined by an ability to dissolve or otherwise harmlessly disappear in environmental or biological surroundings after a period of stable operation. The resulting devices provide unique capabilities as temporary biomedical implants, environmental sensors, and related systems. Recent publications report schemes to overcome challenges in fabrication that follow from the low thermostability and/or high chemical reactivity of the eco/bioresorbable constituent materials. Here, this work reports the use of high-speed sewing machines, as the basis for a high-throughput manufacturing technique that addresses many requirements for these applications, without the need for high temperatures or reactive solvents. Results demonstrate that a range of eco/bioresorbable metal wires and polymer threads can be embroidered into complex, user-defined conductive patterns on eco/bioresorbable substrates. Functional electronic components, such as stretchable interconnects and antennas are possible, along with fully integrated systems. Examples of the latter include wirelessly powered light-emitting diodes, radiofrequency identification tags, and temporary cardiac pacemakers. These advances add to a growing range of options in high-throughput, automated fabrication of eco/bioresorbable electronics.

Speed dependence of thermochemical nanolithography for gray-scale patterning.

Thermochemical nanolithography (TCNL) is a high-resolution lithographic technique and, owing to its fast speed, versatility, and unique ability to fabricate arbitrary, gray-scale nanopatterns, this scanning probe technique is relevant both for fundamental scientific research as well as for nanomanufacturing applications. In this work, we study the dependence of the TCNL driven chemical reactions on the translation speed of the thermal cantilever. The experimental data compares well with a model of the chemical kinetics for a first-order reaction. The impact of higher order reactions on the optimization of TCNL is addressed. The reported quantitative description of the speed dependence of TCNL is exploited and illustrated by fabricating controlled gradients of chemical concentration.

Fabricating nanoscale chemical gradients with ThermoChemical NanoLithography.

Production of chemical concentration gradients on the submicrometer scale remains a formidable challenge, despite the broad range of potential applications and their ubiquity throughout nature. We present a strategy to quantitatively prescribe spatial variations in functional group concentration using ThermoChemical NanoLithography (TCNL). The approach uses a heated cantilever to drive a localized nanoscale chemical reaction at an interface, where a reactant is transformed into a product. We show using friction force microscopy that localized gradients in the product concentration have a spatial resolution of ~20 nm where the entire concentration profile is confined to sub-180 nm. To gain quantitative control over the concentration, we introduce a chemical kinetics model of the thermally driven nanoreaction that shows excellent agreement with experiments. The comparison provides a calibration of the nonlinear dependence of product concentration versus temperature, which we use to design two-dimensional temperature maps encoding the prescription for linear and nonlinear gradients. The resultant chemical nanopatterns show high fidelity to the user-defined patterns, including the ability to realize complex chemical patterns with arbitrary variations in peak concentration with a spatial resolution of 180 nm or better. While this work focuses on producing chemical gradients of amine groups, other functionalities are a straightforward modification. We envision that using the basic scheme introduced here, quantitative TCNL will be capable of patterning gradients of other exploitable physical or chemical properties such as fluorescence in conjugated polymers and conductivity in graphene. The access to submicrometer chemical concentration and gradient patterning provides a new dimension of control for nanolithography.

Detection of infectious influenza virus in cough aerosols generated in a simulated patient examination room.

BACKGROUND: The potential for aerosol transmission of infectious influenza virus (ie, in healthcare facilities) is controversial. We constructed a simulated patient examination room that contained coughing and breathing manikins to determine whether coughed influenza was infectious and assessed the effectiveness of an N95 respirator and surgical mask in blocking transmission. METHODS: National Institute for Occupational Safety and Health aerosol samplers collected size-fractionated aerosols for 60 minutes at the mouth of the breathing manikin, beside the mouth, and at 3 other locations in the room. Total recovered virus was quantitated by quantitative polymerase chain reaction and infectivity was determined by the viral plaque assay and an enhanced infectivity assay. RESULTS: Infectious influenza was recovered in all aerosol fractions (5.0% in >4 µm aerodynamic diameter, 75.5% in 1-4 µm, and 19.5% in <1 µm; n = 5). Tightly sealing a mask to the face blocked entry of 94.5% of total virus and 94.8% of infectious virus (n = 3). A tightly sealed respirator blocked 99.8% of total virus and 99.6% of infectious virus (n = 3). A poorly fitted respirator blocked 64.5% of total virus and 66.5% of infectious virus (n = 3). A mask documented to be loosely fitting by a PortaCount fit tester, to simulate how masks are worn by healthcare workers, blocked entry of 68.5% of total virus and 56.6% of infectious virus (n = 2). CONCLUSIONS: These results support a role for aerosol transmission and represent the first reported laboratory study of the efficacy of masks and respirators in blocking inhalation of influenza in aerosols. The results indicate that a poorly fitted respirator performs no better than a loosely fitting mask.

Local thermomechanical analysis of a microphase-separated thin lamellar PS-b-PEO film.

We use atomic force microscopy (AFM) and hot tip AFM (HT-AFM) to thermophysically characterize a 30 nm thick film of poly(styrene-block-ethylene oxide), PS-b-PEO, and to modify its lamellar patterns having spacing of 39 ± 3 nm. AFM tip scans of the polymer film induce either abrasive surface patterns or nanoscale ripples, which depend upon the tip force, temperature, and number of scans. The evolution of the lamellar patterns is explained by the polymer film molecular structure and mode I crack propagation in the polymer combined with the stick-and-slip behavior of the AFM tip. The HT-AFM measurements at various tip-sample temperatures and scanning speeds yield several thermophysical quantities: the PEO melting temperature of 54 ± 12 °C, the PS glass transition temperature of 54 ± 12 °C, the PS-b-PEO specific heat of 3.6 ± 2.7 J g(-1) K(-1), the PEO melting enthalpy of 111 ± 88 J g(-1), and the free energy of Helmholtz for PEO unfolding (and melting) of 10(-20) J nm(-2). These quantities are obtained for PS-b-PEO volumes of 30,000 nm(3), which correspond to 30 ag of the polymer.

Nanometer-scale flow of molten polyethylene from a heated atomic force microscope tip.

We investigate the nanometer-scale flow of molten polyethylene from a heated atomic force microscope (AFM) cantilever tip during thermal dip-pen nanolithography (tDPN). Polymer nanostructures were written for cantilever tip temperatures and substrate temperatures controlled over the range 100-260 °C and while the tip was either moving with speed 0.5-2.0 µm s(-1) or stationary and heated for 0.1-100 s. We find that polymer flow depends on surface capillary forces and not on shear between tip and substrate. The polymer mass flow rate is sensitive to the temperature-dependent polymer viscosity. The polymer flow is governed by thermal Marangoni forces and non-equilibrium wetting dynamics caused by a solidification front within the feature.

Maskless nanoscale writing of nanoparticle-polymer composites and nanoparticle assemblies using thermal nanoprobes.

Nanoparticle polymer composites containing metal, semiconductor, magnetic, and optically active nanoparticles were deposited onto multiple substrates from a heatable atomic force microscope tip. The nanoparticle nanostructures were functional as deposited or could be etched with an oxygen plasma, revealing single nanoparticle lithographic resolution. Many types of nanoparticles can be patterned with the same technique, without the need to tailor the substrate chemistry and without solution processing.

Micro- and nano-patterned substrates to manipulate cell adhesion.

Cell adhesion to material surfaces regulates host responses to implanted biomaterials and the performance of cell arrays and biotechnological cell culture supports. Therefore, the engineering of substrates that control cell adhesive interactions is critical to the development of bio-interactive interfaces and biotechnological culture supports. We describe the application of advanced fabrication techniques to engineer substrates with well defined chemistry and topography to manipulate cell adhesive interactions. Microcontact printing of self-assembled monolayers and hot embossing imprint lithography approaches were integrated to manipulate focal adhesion assembly, cell adhesion, and cellular spreading and alignment. These micro- and nanopatterned substrates provide useful tools for the analyses of structure-function relationships in adhesive interactions.

Combined microscale mechanical topography and chemical patterns on polymer cell culture substrates.

This paper presents a technique to independently form mechanical topography and surface chemical patterns on polymer cell substrates, and studies the response of osteoblast cells to these surface patterns. The patterns were formed in two separate steps: hot embossing imprint lithography formed the mechanical topography and microcontact printing created the chemical pattern. The resulting substrate had surface features consisting of embossed grooves 4 microm deep and 8 microm wide spaced by 16 microm wide mesas and microcontact printed adhesive lanes 10 microm wide with spacings that ranged from 10 to 100 microm. When presented with either mechanical topography or chemical patterns alone, the cells significantly aligned to the pattern presented. When presented with mechanical topography overlaid with an orthogonal chemical pattern, the cells aligned to the mechanical topography. As the chemical pattern spacing was increased, osteoblasts remained aligned to the mechanical topography. Unlike traditional microfabrication approaches based on photolithography and wet chemistry, the patterning technique presented is compatible with a large number of biomaterials, could form patterns with features much smaller than 1 microm, and is highly scalable to large substrates.

Hot embossing for micropatterned cell substrates.

This paper reports the development of a technique for preparing microtextured polymer substrates for cell growth and studies the response of osteoblast cells grown on these surfaces. The surfaces were manufactured with hot embossing, where a silicon micromachined printing master was pressed into a thermoplastic polymer substrate at elevated temperature, forming a regular microgroove pattern in the polymer. The grooves were approximately 5 microm deep, 4 microm wide, and had a periodicity of 34 microm. The polymer substrate was polyimide, which can be spincast and printed in its uncured form, and is mechanically rigid and chemically nonreactive after full cure. Osteoblast cells were grown on the textured polymer substrate and their responses to grooved and smooth surfaces were observed with fluorescence microscopy. Alignment and aspect ratio were analyzed for the cell body, cell nucleus, and focal adhesions. Cell membrane body, cell nucleus, and focal adhesions all strongly aligned with the microgrooves, while only the cell body shape changed on the microgrooved surface. This novel substrate preparation technique offers the opportunity for low-cost and rapid manufacture of microtextured surfaces that can be used to control cell shape and alignment.

Nanometer-scale infrared spectroscopy of heterogeneous polymer nanostructures fabricated by tip-based nanofabrication.

There is a significant need for chemical identification and chemical imaging of nanofabricated structures and devices, especially for multiple materials integrated at the nanometer scale. Here we present nanofabrication, chemical identification, and nanometer-scale chemical imaging of polymer nanostructures with better than 100 nm spatial resolution. Polymer nanostructures of polyethylene, polystyrene, and poly(3-dodecylthiophene-2,5-diyl) were fabricated by tip-based nanofabrication. Nanometer-scale infrared measurements using atomic force microscopy infrared spectroscopy (AFM-IR) obtained quantitative chemical spectra of these nanostructures. We show chemical imaging of intersecting patterns of nanometer-scale polymer lines of different chemical compositions. The results indicate that for closely packed heterogeneous nanostructures, the spatial resolution of AFM-IR is not limited by nanometer-scale thermal diffusion, but is instead limited by the cantilever sensitivity and the signal-to-noise ratio of the AFM-IR system.

Geometric microenvironment directs cell morphology on topographically patterned hydrogel substrates.

Cell behavior is influenced by numerous factors in the physical environment, and a deep understanding of these interactions can lead to the design of better scaffolds for tissue engineering. In vitro substrates can be used to evaluate a wide range of factors, such as topography, and identify which show promise for further evaluating in vivo. Polyacrylamide hydrogels featuring a combinatorial, micropatterned array of posts with varied shape, width, and spacing were produced using a one-step technique. Substrates were covalently modified with collagen and seeded with D1 ORL UVA mesenchymal stem cells. Patterning was shown to direct several quantitative measures of cell morphology. Cell bodies tended to be located in gaps 15mum and wider, but on top of posts when gaps were 5mum and smaller. Cells on substrates with square posts and narrow gaps tended to elongate in the direction of gaps. Finally, smaller gaps on all substrates were also shown to influence the placement of cell extensions. The parameters identified may be incorporated into substrates to direct specific aspects of cell morphology.

Polymer cell culture substrates with micropatterned carbon nanotubes.

This article presents study of the interactions between cells and micropatterned carbon nanotubes on a polymer cell culture substrate. The polymer substrates with patterned carbon nanotubes were fabricated using an imprint process, whereby the nanotubes were pressed into a polymer layer at high temperature. The patterned substrates featured 28 different nanotube patterns of microscale lanes and circles, where the feature sizes ranged from 9 to 76 microm. Osteoblast-like cells were seeded on the substrates and cell alignment was quantified via fluorescent and electron microscopy. Many patterns were fabricated on each polymer substrate, allowing 28 different experiments on each cell culture substrate, which were tested over 10,000 cells. The cell response to the patterned nanotubes showed a maximum alignment to the microlane patterns of 55 +/- 6% and no significant alignment to microcircle patterns. This work enables the study of cell response to a wider range of patterns featuring both the micro and nano length scales.

Measuring glassy and viscoelastic polymer flow in molecular-scale gaps using a flat punch mechanical probe.

This paper investigates molecular-scale polymer mechanical deformation during large-strain squeeze flow of polystyrene (PS) films, where the squeeze flow gap is close to the polymer radius of gyration (R(g)). Stress-strain and creep relations were measured during flat punch indentation from an initial film thickness of 170 nm to a residual film thickness of 10 nm in the PS films, varying molecular weight (M(w)) and deformation stress rate by over 2 orders of magnitude while temperatures ranged from 20 to 125 degrees C. In stress-strain curves exhibiting an elastic-to-plastic yield-like knee, the response was independent of M(w), as expected from bulk theory for glassy polymers. At high temperatures and long times sufficient to extinguish the yield-knee, the mechanical response M(w) degeneracy was broken, but no molecular confinement effects were observed during thinning. Creep measurements in films of 44K M(w) were well-approximated by bulk Newtonian no-slip flow predictions. For extrusions down to a film thickness of 10 nm, the mechanical relaxation in these polymer films scaled with temperature similar to Williams-Landel-Ferry scaling in bulk polymer. Films of 9000K M(w), extruded from an initial film thickness of 2R(g) to a residual film thickness of 0.5R(g), while showing stress-strain viscoelastic response similar to that of films of 900K M(w), suggestive of shear-thinning behavior, could not be matched to a constitutive flow model. In general, loading rate and magnitude influenced subsequent creep extrusion depth of high-M(w) films, with deeper final extrusions for high loading rates than for low loading rates. The measurements suggest that, for high-resolution nanoimprint lithography, mold flash or final residual film thickness can be reduced for high strain and strain rate loading of high-M(w) thin films.

High-speed, sub-15 nm feature size thermochemical nanolithography.

We report a nanolithography technique that allows simultaneous direct control of the local chemistry and topography of thin polymer films. Specifically, a heated atomic force microscope (AFM) tip can write sub-15 nm hydrophilic features onto a hydrophobic polymer at the rate of 1.4 mm per s. The thermally activated chemical reactions and topography changes depend on the chemical composition of the polymer, the raster speed, the temperature at the AFM tip/sample interface, and the normal load. This method is conceptually simple, direct, extremely rapid, achievable in a range of environments, and potentially adaptable to other materials systems.