Selective Autonomous Molecular Transport and Collection by Hydrogel-Embedded Supramolecular Chemical Gradients.

Selective transport and concentration of molecules to specified regions on a substrate both enhances the potential to detect such molecules and provides a path to spatially localize such molecules prior to initiation of subsequent chemical reactions. Here, we first embed radially symmetric α-, ß-, and γ-cyclodextrin gradients in a hydrogel matrix. Driven by host-guest interactions between the cyclodextrins and the target molecule, we observe these gradients can serve to direct 2D molecular transport. Using xanthene dyes and organophosphates as target molecules, we found the transport metrics, e.g., selectivity, rate, and concentration limits, are strongly dependent on the specific cyclodextrin forming the gradient. In all cases, as the concentrating power of the gradient increased, the rate of target concentration slowed, which we hypothesize is because stronger interactions between the target and the cyclodextrin decrease the rate of target diffusion. The concentration enhancement for the nerve agent simulant 4-methylumbelliferyl phosphate (15.8) is the greatest when the gradient is formed using ß-cyclodextrin while directed concentration of cyanomethyl phosphonate, a smaller non-aromatic organophosphate, is observed only for the smaller α-CD. To provide a near real-time read-out of the concentration of the analyte, we used an array of IR resonant metallic nanoantennas tuned to a specific IR absorption band of the analyte to enhance the IR signal generated by the analyte.

Mechanisms, Capabilities, and Applications of High-Resolution Electrohydrodynamic Jet Printing.

This review gives an overview of techniques used for high-resolution jet printing that rely on electrohydrodynamically induced flows. Such methods enable the direct, additive patterning of materials with a resolution that can extend below 100 nm to provide unique opportunities not only in scientific studies but also in a range of applications that includes printed electronics, tissue engineering, and photonic and plasmonic devices. Following a brief historical perspective, this review presents descriptions of the underlying processes involved in the formation of liquid cones and jets to establish critical factors in the printing process. Different printing systems that share similar principles are then described, along with key advances that have been made in the last decade. Capabilities in terms of printable materials and levels of resolution are reviewed, with a strong emphasis on areas of potential application.

Fundamental Limits in Combine Harvester Header Height Control.

This paper investigates fundamental performance limitations in the control of a combine harvester's header height control system. There are two primary subsystem characteristics that influence the achievable bandwidth by affecting the open loop transfer function. The first subsystem is the mechanical configuration of the combine and header while the second subsystem is the electrohydraulic actuation for the header. The mechanical combine + header subsystem results in an input-output representation that is underactuated and has a noncollocated sensor/actuator pair. The electrohydraulic subsystem introduces a significant time delay. In combination, they each reinforce the effect of the other thereby exacerbating the overall system limitation of the closed loop bandwidth. Experimental results are provided to validate the model and existence of the closed loop bandwidth limitations that stem from specific system design configurations.

Functional protein microarrays by electrohydrodynamic jet printing.

This paper reports the use of advanced forms of electrohydrodynamic jet (e-jet) printing for creating micro- and nanoscale patterns of proteins on various surfaces ranging from flat silica substrates to structured plasmonic crystals, suitable for micro/nanoarray analysis and other applications in both fluorescent and plasmonic detection modes. The approaches function well with diverse classes of proteins, including streptavidin, IgG, fibrinogen, and γ-globulin. Detailed study reveals that the printing process does not adversely alter the protein structure or function, as demonstrated in the specific case of streptavidin through measurements of its binding specificity to biotin-modified DNA. Multinozzle printing systems enable several types of proteins (up to four currently) to be patterned on a single substrate, in rapid fashion and with excellent control over spatial dimensions and registration. High-speed, pulsed operational modes allow large-area printing, with narrow statistical distributions of drop size and spacing in patterns that include millions of droplets. The process is also compatible with the structured surfaces of plasmonic crystal substrates to enable detection without fluorescence. These collective characteristics suggest potential utility of e-jet techniques in wide-ranging areas of biotechnology, where its compatibility with various biomaterials and substrates with different topographies and surface chemistries, and ability to form deposits that range from thick films to submonolayer coatings, derive from the remote, noncontacting physical material transfer mode of operation.

Design and manufacture of combinatorial calcium phosphate bone scaffolds.

It is well known that pore design is an important determinant of both the quantity and distribution of regenerated bone in artificial bone tissue scaffolds. A requisite feature is that scaffolds must contain pore interconnections on the order of 100-1000 µm (termed macroporosity). Within this range, there is not a definitive optimal interconnection size. Recent results suggest that pore interconnections permeating the scaffold build material on the order of 2-20 µm (termed microporosity) drive bone growth into the macropore space at a faster rate and also provide a new space for bone growth, proliferating throughout the interconnected microporous network. The effects of microstructural features on bone growth has yet to be fully understood. This work presents the manufacture and characterization of novel combinatorial test scaffolds, scaffolds that test multiple microporosity and macroporosity designs within a single scaffold. Scaffolds such as this can efficiently evaluate multiple mechanical designs, with the advantage of having the designs colocated within a single defect site and therefore less susceptible to experimental variation. This paper provides the manufacturing platform, manufacturing control method, and demonstrates the manufacturing capabilities with three representative scaffolds.

Nanostructured jumping-droplet thermal rectifier.

Analogous to an electrical rectifier, a thermal rectifier (TR) can ensure that heat flows in a preferential direction. In this paper, thermal transport nonlinearity is achieved through the development of a phase-change based TR comprising an enclosed vapor chamber having separated nanostructured copper oxide superhydrophobic and superhydrophilic functional surfaces. In the forward direction, heat transfer is facilitated through evaporation on the superhydrophilic surface and self-propelled jumping-droplet condensation on the superhydrophobic surface. In the reverse direction, heat transfer is minimized due to condensate film formation within the superhydrophilic condenser and inability to return the condensed liquid to the superhydrophobic evaporator. We examine the coupled effects of gap size, coolant mass, heat transfer rate, and applied electric field on the thermal performance of the TR. A maximum thermal diodicity, defined as the ratio of forward to reverse heat transfer, of 39 is achieved.

1D and 2D error assessment and correction for extrusion-based bioprinting using process sensing and control strategies.

The bioprinting literature currently lacks: (i) process sensing tools to measure material deposition, (ii) performance metrics to evaluate system performance, and (iii) control tools to correct for and avoid material deposition errors. The lack of process sensing tools limits in vivo functionality of bioprinted parts since accurate material deposition is critical to mimicking the heterogeneous structures of native tissues. We present a process monitoring and control strategy for extrusion-based fabrication that addresses all three gaps to improve material deposition. Our strategy uses a non-contact laser displacement scanner that measures both the spatial material placement and width of the deposited material. We developed a custom image processing script that uses the laser scanner data and defined error metrics for assessing material deposition. To implement process control, the script uses the error metrics to modify control inputs for the next deposition iteration in order to correct for the errors. A key contribution is the definition of a novel method to quantitatively evaluate the accuracy of printed constructs. We implement the process monitoring and control strategy on an extrusion-printing system to evaluate system performance and demonstrate improvement in both material placement and material width.

Direct process feedback in extrusion-based 3D bioprinting.

A major limitation in extrusion-based bioprinting is the lack of direct process control, which limits the accuracy and design complexity of printed constructs. The lack of direct process control results in a number of defects that can influence the functional and mechanical outcomes of the fabricated structures. The machine axes motion cannot be reliably used to predict material placement, and precise fabrication requires additional sensing of the material extrusion. We present an iteration-to-iteration process monitoring system that enables direct process control in the material deposition reference frame. To fabricate parts with low dimensional errors, we integrate a non-contact laser displacement scanner into the printing platform. After fabrication of the initial print using the as-designed reference trajectory, the laser scanner moves across the part to measure the material placement. A custom image processing algorithm compares the laser scanner data to the as-designed reference trajectory to generate an error vector. To compensate for the measured error, the algorithm modifies the axes reference trajectory for the second print iteration. We implement the in situ process monitoring and error compensation technique on an experimental platform to evaluate system performance and demonstrate improvement in spatial material placement.

Micro-robotic deposition guidelines by a design of experiments approach to maximize fabrication reliability for the bone scaffold application.

This work aims to facilitate the transition of micro-robotic deposition (microRD) technology from the research bench to a mass manufacturing environment. The bone scaffolding application is targeted; however, the evaluation process developed is applicable to multiple colloidal material systems, length scales, and structure architectures. A design of experiments (DoE) approach is used to develop statistical correlations between three manufacturing treatments (material calcination time, nozzle size, and deposition speed) and defined reliability metrics. All three selected treatments have a significant effect on structure quality. A longer material calcination time improves the deposition of internal features. Logically, a larger nozzle size decreases structural defects. However, an unexpected result is revealed by this study. Higher deposition speeds are shown to either significantly improve or have no effect on structure quality, permitting a decrease in manufacturing time without adverse consequences.

Directed Molecular Collection by E-Jet Printed Microscale Chemical Potential Wells in Hydrogel Films.

A facile approach to locally concentrate analytes of interest will significantly enhance miniaturized, integrated chemical-analysis systems. Here, the directed analyte transport and concentration using ≈200 µm-diameter E-jet printed chemical potential wells in a polyacrylamide hydrogel is demonstrated. Using a cationic well as the model system, anionic analytes are accumulated into a microscale area with a local concentration enhancement of >50-fold relative to the surrounding area. By downscaling the diameter of the chemical potential well from a few millimeters to 100s of micrometers, it is found, using both fluorescence and Raman microscopy, that the molecular collection capacity of the well is greatly improved. Additionally, it is shown that molecules can be simultaneously transported and concentrated to arrays of microscale regions using an array of microscale chemical potential wells. This approach enhances many-fold the limit of detection, enables the formation of microscale potential well arrays with a variety of chemical properties, and provides a novel microscale molecular manipulation technique as an alternative to traditional microfluidic-based systems.

Net shape fabrication of calcium phosphate scaffolds with multiple material domains.

Calcium phosphate (CaP) materials have been proven to be efficacious as bone scaffold materials, but are difficult to fabricate into complex architectures because of the high processing temperatures required. In contrast, polymeric materials are easily formed into scaffolds with near-net-shape forms of patient-specific defects and with domains of different materials; however, they have reduced load-bearing capacity compared to CaPs. To preserve the merits of CaP scaffolds and enable advanced scaffold manufacturing, this manuscript describes an additive manufacturing process that is coupled with a mold support for overhanging features; we demonstrate that this process enables the fabrication of CaP scaffolds that have both complex, near-net-shape contours and distinct domains with different microstructures. First, we use a set of canonical structures to study the manufacture of complex contours and distinct regions of different material domains within a mold. We then apply these capabilities to the fabrication of a scaffold that is designed for a 5 cm orbital socket defect. This scaffold has complex external contours, interconnected porosity on the order of 300 µm throughout, and two distinct domains of different material microstructures.

Photonic crystal enhancement of a homogeneous fluorescent assay using submicron fluid channels fabricated by E-jet patterning.

We demonstrate the enhancement of a liquid-based homogenous fluorescence assay using the resonant electric fields from a photonic crystal (PC) surface. Because evanescent fields are confined to the liquid volume nearest to the photonic crystal, we developed a simple approach for integrating a PC fabricated on a silicon substrate within a fluid channel with submicron height, using electrohydrodynamic jet (e-jet) printing of a light-curable epoxy adhesive to define the fluid channel pattern. The PC is excited by a custom-designed compact instrument that illuminates the PC with collimated light that precisely matches the resonant coupling condition when the PC is covered with aqueous media. Using a molecular beacon nucleic acid fluorescence resonant energy transfer (FRET) probe for a specific miRNA sequence, we demonstrate an 8× enhancement of the fluorescence emission signal, compared to performing the same assay without exciting resonance in the PC detecting a miRNA sequence at a concentration of 62 nM from a liquid volume of only ∼20 nL. The approach may be utilized for any liquid-based fluorescence assay for applications in point-of-care diagnostics, environmental monitoring, or pathogen detection.

Block copolymer assembly on nanoscale patterns of polymer brushes formed by electrohydrodynamic jet printing.

Fundamental understanding of the self-assembly of domains in block copolymers (BCPs) and capabilities in control of these processes are important for their use as nanoscale templates in various applications. This paper focuses on the self-assembly of spin-cast and printed poly(styrene-block-methyl methacrylate) BCPs on patterned surface wetting layers formed by electrohydrodynamic jet printing of random copolymer brushes. Here, end-grafted brushes that present groups of styrene and methyl methacrylate in geometries with nanoscale resolution deterministically define the morphologies of BCP nanostructures. The materials and methods can also be integrated with lithographically defined templates for directed self-assembly of BCPs at multiple length scales. The results provide not only engineering routes to controlled formation of complex patterns but also vehicles for experimental and simulation studies of the effects of chemical transitions on the processes of self-assembly. In particular, we show that the methodology developed here provides the means to explore exotic phenomena displayed by the wetting behavior of BCPs, where 3-D soft confinement, chain elasticity, interfacial energies, and substrate's surface energy cooperate to yield nonclassical wetting behavior.

Hierarchical patterns of three-dimensional block-copolymer films formed by electrohydrodynamic jet printing and self-assembly.

Self-assembly of block-copolymers provides a route to the fabrication of small (size, <50 nm) and dense (pitch, <100 nm) features with an accuracy that approaches even the demanding specifications for nanomanufacturing set by the semiconductor industry. A key requirement for practical applications, however, is a rapid, high-resolution method for patterning block-copolymers with different molecular weights and compositions across a wafer surface, with complex geometries and diverse feature sizes. Here we demonstrate that an ultrahigh-resolution jet printing technique that exploits electrohydrodynamic effects can pattern large areas with block-copolymers based on poly(styrene-block-methyl methacrylate) with various molecular weights and compositions. The printed geometries have diameters and linewidths in the sub-500 nm range, line edge roughness as small as ∼45 nm, and thickness uniformity and repeatability that can approach molecular length scales (∼2 nm). Upon thermal annealing on bare, or chemically or topographically structured substrates, such printed patterns yield nanodomains of block-copolymers with well-defined sizes, periodicities and morphologies, in overall layouts that span dimensions from the scale of nanometres (with sizes continuously tunable between 13 nm and 20 nm) to centimetres. As well as its engineering relevance, this methodology enables systematic studies of unusual behaviours of block-copolymers in geometrically confined films.

High bandwidth control of precision motion instrumentation.

This article presents a high-bandwidth control design suitable for precision motion instrumentation. Iterative learning control (ILC), a feedforward technique that uses previous iterations of the desired trajectory, is used to leverage the repetition that occurs in many tasks, such as raster scanning in microscopy. Two ILC designs are presented. The first design uses the motion system dynamic model to maximize bandwidth. The second design uses a time-varying bandwidth that is particularly useful for nonsmooth trajectories such as raster scanning. Both designs are applied to a multiaxis piezoelectric-actuated flexure system and evaluated on a nonsmooth trajectory. The ILC designs demonstrate significant bandwidth and precision improvements over the feedback controller, and the ability to achieve precision motion control at frequencies higher than multiple system resonances.

High-resolution electrohydrodynamic jet printing.

Efforts to adapt and extend graphic arts printing techniques for demanding device applications in electronics, biotechnology and microelectromechanical systems have grown rapidly in recent years. Here, we describe the use of electrohydrodynamically induced fluid flows through fine microcapillary nozzles for jet printing of patterns and functional devices with submicrometre resolution. Key aspects of the physics of this approach, which has some features in common with related but comparatively low-resolution techniques for graphic arts, are revealed through direct high-speed imaging of the droplet formation processes. Printing of complex patterns of inks, ranging from insulating and conducting polymers, to solution suspensions of silicon nanoparticles and rods, to single-walled carbon nanotubes, using integrated computer-controlled printer systems illustrates some of the capabilities. High-resolution printed metal interconnects, electrodes and probing pads for representative circuit patterns and functional transistors with critical dimensions as small as 1 mum demonstrate potential applications in printed electronics.

Stamp collapse in soft lithography.

We have studied the so-called roof collapse in soft lithography. Roof collapse is due to the adhesion between the PDMS stamp and substrate, and it may affect the quality of soft lithography. Our analysis accounts for the interactions of multiple punches and the effect of elastic mismatch between the PDMS stamp and substrate. A scaling law among the stamp modulus, punch height and spacing, and work of adhesion between the stamp and substrate is established. Such a scaling law leads to a simple criterion against the unwanted roof collapse. The present study agrees well with the experimental data.