Iterative Patient Testing of a Stimuli-Responsive Swallowing Activity Sensor to Promote Extended User Engagement During the First Year After Radiation: Multiphase Remote and In-Person Observational Cohort Study.

BACKGROUND: Frequent sensor-assisted monitoring of changes in swallowing function may help improve detection of radiation-associated dysphagia before it becomes permanent. While our group has prototyped an epidermal strain/surface electromyography sensor that can detect minute changes in swallowing muscle movement, it is unknown whether patients with head and neck cancer would be willing to wear such a device at home after radiation for several months. OBJECTIVE: We iteratively assessed patients' design preferences and perceived barriers to long-term use of the prototype sensor. METHODS: In study 1 (questionnaire only), survivors of pharyngeal cancer who were 3-5 years post treatment and part of a larger prospective study were asked their design preferences for a hypothetical throat sensor and rated their willingness to use the sensor at home during the first year after radiation. In studies 2 and 3 (iterative user testing), patients with and survivors of head and neck cancer attending visits at MD Anderson's Head and Neck Cancer Center were recruited for two rounds of on-throat testing with prototype sensors while completing a series of swallowing tasks. Afterward, participants were asked about their willingness to use the sensor during the first year post radiation. In study 2, patients also rated the sensor's ease of use and comfort, whereas in study 3, preferences were elicited regarding haptic feedback. RESULTS: The majority of respondents in study 1 (116/138, 84%) were willing to wear the sensor 9 months after radiation, and participant willingness rates were similar in studies 2 (10/14, 71.4%) and 3 (12/14, 85.7%). The most prevalent reasons for participants' unwillingness to wear the sensor were 9 months being excessive, unwanted increase in responsibility, and feeling self-conscious. Across all three studies, the sensor's ability to detect developing dysphagia increased willingness the most compared to its appearance and ability to increase adherence to preventive speech pathology exercises. Direct haptic signaling was also rated highly, especially to indicate correct sensor placement and swallowing exercise performance. CONCLUSIONS: Patients and survivors were receptive to the idea of wearing a personalized risk sensor for an extended period during the first year after radiation, although this may have been limited to well-educated non-Hispanic participants. A significant minority of patients expressed concern with various aspects of the sensor's burden and its appearance. TRIAL REGISTRATION: ClinicalTrials.gov NCT03010150; https://clinicaltrials.gov/study/NCT03010150.

Synthesis of PEDOT:PSS Brushes Grafted from Gold Using ATRP for Increased Electrochemical and Mechanical Stability.

We report PEDOT:PSS brushes grafted from gold using surface-initiated atom-transfer radical polymerization (SI-ATRP) which demonstrate significantly enhanced mechanical stability against sonication and electrochemical cycling compared to spin-coated analogues as well as lower impedances than bare gold at frequencies from 0.1 to 105 Hz. These results suggest SI-ATRP PEDOT:PSS to be a promising candidate for use in microelectrodes for neural activity recording. Spin-coated, electrodeposited, and drop-cast PEDOT:PSS have already been shown to reduce impedance and improve biocompatibility of microelectrodes, but the lack of strong chemical bonds of the physisorbed polymer film to the metal leads to disintegration under required operational stresses including cyclic mechanical loads, abrasion, and electrochemical cycling. Rather than modifying the metal electrode or introducing cross-linkers or other additives to improve the stability of the polymer film, this work chemically tethers the polymer to the surface, offering a simple, scalable solution for functional bioelectronic interfaces.

Effect of Additives on the Surface Morphology, Energetics, and Contact Resistance of PEDOT:PSS.

For a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) film employed in a device stack, charge must pass through both the bulk of the film and interfaces between adjacent layers. Thus, charge transport is governed by both bulk and contact resistances. However, for ultrathin films (e.g., flexible devices, thin-film transistors, printed electronics, solar cells), interfacial properties can dominate over the bulk properties, making contact resistance a significant determinant of device performance. For most device applications, the bulk conductivity of PEDOT:PSS is typically improved by blending additives into the solid film. Doping PEDOT:PSS with secondary dopants (e.g., polar small molecules), in particular, increases the bulk conductivity by inducing a more favorable solid morphology. However, the effects of these morphological changes on the contact resistance (which play a bigger role at smaller length scales) are relatively unstudied. In this work, we use transfer length method (TLM) measurements to decouple the bulk resistance from the contact resistance of PEDOT:PSS films incorporating several common additives. These additives include secondary dopants, a silane crosslinker (typically used to stabilize the PEDOT:PSS film), and multi-walled carbon nanotubes (conductive fillers). Using conductive atomic force microscopy, Kelvin probe force microscopy, Raman spectroscopy, and photoelectron spectroscopy, we connect changes in the contact resistance to changes in the surface morphology and energetics as governed by the blended additives. We find that the contact resistance at the PEDOT:PSS/silver interface can be reduced by (1) increasing the ratio of PEDOT to PSS chains, (2) decreasing the work function, (3) decreasing the benzoid-to-quinoid ratio at the surface of the solid film, (4) increasing the film uniformity and contact area, and (5) increasing the phase-segregated morphology of the solid film.

Tailoring Molecular-Scale Contact at the Perovskite/Polymeric Hole-Transporting Material Interface for Efficient Solar Cells.

Perovskite solar cells (PSCs) have delivered a power conversion efficiency (PCE) of more than 25% and incorporating polymers as hole-transporting layers (HTLs) can further enhance the stability of devices toward the goal of commercialization. Among the various polymeric hole-transporting materials, poly(triaryl amine) (PTAA) is one of the promising HTL candidates with good stability; however, the hydrophobicity of PTAA causes problematic interfacial contact with the perovskite, limiting the device performance. Using molecular side-chain engineering, a uniform 2D perovskite interlayer with conjugated ligands, between 3D perovskites and PTAA is successfully constructed. Further, employing conjugated ligands as cohesive elements, perovskite/PTAA interfacial adhesion is significantly improved. As a result, the thin and lateral extended 2D/3D heterostructure enables as-fabricated PTAA-based PSCs to achieve a PCE of 23.7%, improved from the 18% of reference devices. Owing to the increased ion-migration energy barrier and conformal 2D coating, unencapsulated devices with the new ligands exhibit both superior thermal stability under 60 °C heating and moisture stability in ambient conditions.

Decoupling Planarizing and Steric Energetics to Accurately Model the Rigidity of π-Conjugated Polymers.

The π-conjugated backbone of semiconducting polymers gives rise to both their electronic properties and structural rigidity. However, current computational methods for understanding the rigidity of polymer chains fail in one crucial way. Namely, standard torsional scan (TS) methods do not satisfactorily capture the behavior of polymers exhibiting a high degree of steric hindrance. This deficiency in part stems from the method by which torsional scans decouple energy related to electron delocalization from that related to nonbonded interactions. These methods do so by applying classical corrections of the nonbonded energy to the quantum mechanical (QM) torsional profile for polymers that are highly sterically hindered. These large corrections to the energy from nonbonded interactions can substantially skew the calculated QM energies related to torsion, resulting in an inaccurate or imprecise estimation of the rigidity of a polymer. As a consequence, simulations of the morphology of a highly sterically hindered polymer using the TS method can be highly inaccurate. Here, we describe an alternative, generalizable method by which the delocalization energy can be decoupled from the energy associated with nonbonded interactions─the "isolation of delocalization energy" (DE) method. From torsional energy calculations, we find that the relative accuracy of the DE method is similar to the TS method (within 1 kJ/mol) for two model polymers (P3HT, PTB7) when compared to quantum mechanical calculations. However, the DE method significantly increased the relative accuracy for simulations of PNDI-T, a highly sterically hindered polymer (8.16 kJ/mol). Likewise, we show that comparison of the planarization energy (i.e., backbone rigidity) from torsional parameters is significantly more precise for both PTB7 and PNDI-T when using the DE method as opposed to the TS method. These differences affect the simulated morphology, with the DE method predicting a significantly more planar configuration of PNDI-T.

Solvent-Free Transfer of Freestanding Large-Area Conjugated Polymer Films for Optoelectronic Applications.

Conventional processes for depositing thin films of conjugated polymers are restricted to those based on vapor, liquid, and solution-phase precursors. Each of these methods bear some limitations. For example, low-bandgap polymers with alternating donor-acceptor structures cannot be deposited from the vapor phase, and solution-phase deposition is always subject to issues related to the incompatibility of the substrate with the solvent. Here, a technique to enable deposition of large-area, ultra-thin films (≈20 nm or more), which are transferred from the surface of water, is demonstrated. From the water, these pre-solidified films can then be transferred to a desired substrate, circumventing limitations such as solvent orthogonality. The quality of these films is characterized by a variety of imaging and electrochemical measurements. Mechanical toughness is identified as a limiting property of polymer compatibility, along with some strategies to address this limitation. As a demonstration, the films are used as the hole-transport layer in perovskite solar cells, in which their performance is shown to be comparable to controls formed by spin-coating.

Multiple pathways to stretchable electronics.

Stretchable conductors expand the interfaces with biological structures.

Intrinsically Stretchable Block Copolymer Based on PEDOT:PSS for Improved Performance in Bioelectronic Applications.

The conductive polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is ubiquitous in research dealing with organic electronic devices (e.g., solar cells, wearable and implantable sensors, and electrochemical transistors). In many bioelectronic applications, the applicability of commercially available formulations of PEDOT:PSS (e.g., Clevios) is limited by its poor mechanical properties. Additives can be used to increase the compliance but pose a risk of leaching, which can result in device failure and increased toxicity (in biological settings). Thus, to increase the mechanical compliance of PEDOT:PSS without additives, we synthesized a library of intrinsically stretchable block copolymers. In particular, controlled radical polymerization using a reversible addition-fragmentation transfer process was used to generate block copolymers consisting of a block of PSS (of fixed length) appended to varying blocks of poly(poly(ethylene glycol) methyl ether acrylate) (PPEGMEA). These block copolymers (PSS(1)-b-PPEGMEA(x), where x ranges from 1 to 6) were used as scaffolds for oxidative polymerization of PEDOT. By increasing the lengths of the PPEGMEA segments on the PEDOT:[PSS(1)-b-PPEGMEA(1-6)] block copolymers, ("Block-1" to "Block-6"), or by blending these copolymers with PEDOT:PSS, the mechanical and electronic properties of the polymer can be tuned. Our results indicate that the polymer with the longest block of PPEGMEA, Block-6, had the highest fracture strain (75%) and lowest elastic modulus (9.7 MPa), though at the expense of conductivity (0.01 S cm-1). However, blending Block-6 with PEDOT:PSS to compensate for the insulating nature of the PPEGMEA resulted in increased conductivity [2.14 S cm-1 for Blend-6 (2:1)]. Finally, we showed that Block-6 outperforms a commercial formulation of PEDOT:PSS as a dry electrode for surface electromyography due to its favorable mechanical properties and better adhesion to skin.

Polymer Chemistry for Haptics, Soft Robotics, and Human-Machine Interfaces.

Progress in the field of soft devices-i.e., haptics, robotics, and human-machine interfaces (HRHMIs)-has its basis in the science of polymeric materials and chemical synthesis. However, in examining the relevant literature, we find that most developments have been enabled by off-the-shelf materials used either alone or as components of physical blends and composites. In this Progress Report, we take the position that a greater awareness of the capabilities of synthetic chemistry will accelerate the capabilities of HRHMIs. Conversely, an awareness of the applications sought by engineers working in this area may spark the development of new molecular designs and synthetic methodologies by chemists. We highlight several applications of active, stimuli-responsive polymers, which have demonstrated or shown potential use in HRHMIs. These materials share the fact that they are products of state-of-the-art synthetic techniques. The Progress Report is thus organized by the chemistry by which the materials were synthesized, including controlled radical polymerization, metal-mediated cross-coupling polymerization, ring-opening polymerization, various strategies for crosslinking, and hybrid approaches. These methods can afford polymers with multiple properties (i.e. conductivity, stimuli-responsiveness, self-healing and degradable abilities, biocompatibility, adhesiveness, and mechanical robustness) that are of great interest to scientists and engineers concerned with soft devices for human interaction.

Comparison of the Mechanical Properties of a Conjugated Polymer Deposited Using Spin Coating, Interfacial Spreading, Solution Shearing, and Spray Coating.

The mechanical properties of π-conjugated (semiconducting) polymers are a key determinant of the stability and manufacturability of devices envisioned for applications in energy and healthcare. These properties─including modulus, extensibility, toughness, and strength─are influenced by the morphology of the solid film, which depends on the method of processing. To date, the majority of work done on the mechanical properties of semiconducting polymers has been performed on films deposited by spin coating, a process not amenable to the manufacturing of large-area films. Here, we compare the mechanical properties of thin films of regioregular poly(3-heptylthiophene) (P3HpT) produced by three scalable deposition processes─interfacial spreading, solution shearing, and spray coating─and spin coating (as a reference). Our results lead to four principal conclusions. (1) Spray-coated films have poor mechanical robustness due to defects and inhomogeneous thickness. (2) Sheared films show the highest modulus, strength, and toughness, likely resulting from a decrease in free volume. (3) Interfacially spread films show a lower modulus but greater fracture strain than spin-coated films. (4) The trends observed in the tensile behavior of films cast using different deposition processes held true for both P3HpT and poly(3-butylthiophene) (P3BT), an analogue with a higher glass transition temperature. Grazing incidence X-ray diffraction and ultraviolet-visible spectroscopy reveal many notable differences in the solid structures of P3HpT films generated by all four processes. While these morphological differences provide possible explanations for differences in the electronic properties (hole mobility), we find that the mechanical properties of the film are dominated by the free volume and surface topography. In field-effect transistors, spread films had mobilities more than 1 magnitude greater than any other films, likely due to a relatively high proportion of edge-on texturing and long coherence length in the crystalline domains. Overall, spread films offer the best combination of deformability and charge-transport properties.

Survival of polymeric microstructures subjected to interrogatory touch.

Polymeric arrays of microrelief structures have a range of potential applications. For example, to influence wettability, to act as biologically inspired adhesives, to resist biofouling, and to play a role in the "feel" of an object during tactile interaction. Here, we investigate the damage to micropillar arrays comprising pillars of different modulus, spacing, diameter, and aspect ratio due to the sliding of a silicone cast of a human finger. The goal is to determine the effect of these parameters on the types of damage observed, including adhesive failure and ploughing of material from the finger onto the array. Our experiments point to four principal conclusions [1]. Aspect ratio is the dominant parameter in determining survivability through its effect on the bending stiffness of micropillars [2]. All else equal, micropillars with larger diameter are less susceptible to breakage and collapse [3]. The spacing of pillars in the array largely determines which type of adhesive failure occurs in non-surviving arrays [4]. Elastic modulus plays an important role in survivability. Clear evidence of elastic recovery was seen in the more flexible polymer and this recovery led to more instances of pristine survivability where the stiffer polymer tended to ablate PDMS. We developed a simple model to describe the observed bending of micropillars, based on the quasi-static mechanics of beam-columns, that indicated they experience forces ranging from 10-4-10-7 N to deflect into adhesive contact. Taken together, results obtained using our framework should inform design considerations for microstructures intended to be handled by human users.

Printing Multi-Material Organic Haptic Actuators.

Haptic actuators generate touch sensations and provide realism and depth in human-machine interactions. A new generation of soft haptic interfaces is desired to produce the distributed signals over large areas that are required to mimic natural touch interactions. One promising approach is to combine the advantages of organic actuator materials and additive printing technologies. This powerful combination can lead to devices that are ergonomic, readily customizable, and economical for researchers to explore potential benefits and create new haptic applications. Here, an overview of emerging organic actuator materials and digital printing technologies for fabricating haptic actuators is provided. In particular, the focus is on the challenges and potential solutions associated with integration of multi-material actuators, with an eye toward improving the fidelity and robustness of the printing process. Then the progress in achieving compact, lightweight haptic actuators by using an open-source extrusion printer to integrate different polymers and composites in freeform designs is reported. Two haptic interfaces-a tactile surface and a kinesthetic glove-are demonstrated to show that printing with organic materials is a versatile approach for rapid prototyping of various types of haptic devices.

Electropneumotactile Stimulation: Multimodal Haptic Actuators Enabled by a Stretchable Conductive Polymer on Inflatable Pockets.

This paper describes a type of haptic device that delivers two modes of stimulation simultaneously and at the same locations on the skin. The two modes of stimulation are mechanical (delivered pneumatically by inflatable air pockets embedded within a silicone elastomer) and electrical (delivered by a conductive polymer). The key enabling aspect of this work is the use of a highly plasticized conductive polymer based on poly(3,4-ethylenedioxythiphene) (PEDOT) blended with elastomeric polyurethane (PU). To fabricate the "electropneumotactile" device, the polymeric electrodes are overlaid directly on top of the elastomeric pneumatic actuator pockets. Co-placement of the pneumatic actuators and the electrotactile electrodes is enabled by the stretchability of the PEDOT:OTs/PU blend, allowing the electrotactiles to conform to underlying pneumatic pockets under deformation. The blend of PEDOT and PU has a Young's modulus of ~150 MPa with little degradation in conductivity following repeated inflation of the air pockets. The ability to perceive simultaneous delivery of two sensations to the same location on the skin are supported by experiments using human subjects. These results show that participants can successfully detect the location of pneumatic stimulation and whether electrotactile stimulation is delivered (yes/no) at a rate significantly above chance (mean accuracy = 94%).

Metallic Nanoislands on Graphene for Biomechanical Sensing.

This minireview describes a nanomaterial-based multimodal sensor for performing biomechanical measurements. The sensor consists of ultrathin metallic films on single-layer graphene. This composite material exhibits physical properties that neither material possesses alone. For example, the metal, deposited by evaporation at low (≤10 nm) nominal thicknesses, renders the film highly sensitive to mechanical stimuli, which can be detected using electrical (i.e., resistance) and optical (i.e., plasmonic) modalities. The electrical modality, in particular, is capable of resolving deformations as small as 0.0001% engineering strain, or 1 ppm. The electrical and optical responses of the composite films can be tailored by controlling the morphology of the metallic film. This morphology (granular or island-like when deposited onto the graphene) can be tuned using the conditions of deposition, the identity of the substrate beneath the graphene, or even the replacement of the graphene for hexagonal boron nitride (hBN). This material responds to forces produced by a range of physiological structures, from the contractions of heart muscle cells, to the beating of the heart through the skin, to stretching of the skin due to the expansion of the lungs and movement of limbs. Here, we provide an update on recent applications of this material in fields ranging from cardiovascular medicine (by measuring the contractions of 2D monolayers of cardiomyocytes), regenerative medicine (optical measurements of the forces produced by myoblasts), speech pathology and physical therapy (measuring swallowing function in head and neck cancer survivors), lab-on-a-chip devices (using deformation of sidewalls of microfluidic channels to detect transiting objects), and sleep medicine (measuring pulse and respiration with a wearable, unobtrusive device). We also discuss the mechanisms by which these films detect strain.

Virtual Texture Generated using Elastomeric Conductive Block Copolymer in Wireless Multimodal Haptic Glove.

Haptic devices are in general more adept at mimicking the bulk properties of materials than they are at mimicking the surface properties. This paper describes a haptic glove capable of producing sensations reminiscent of three types of near-surface properties: hardness, temperature, and roughness. To accomplish this mixed mode of stimulation, three types of haptic actuators were combined: vibrotactile motors, thermoelectric devices, and electrotactile electrodes made from a stretchable conductive polymer synthesized in our laboratory. This polymer consisted of a stretchable polyanion which served as a scaffold for the polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT). The scaffold was synthesized using controlled radical polymerization to afford material of low dispersity, relatively high conductivity (0.1 S cm-1), and low impedance relative to metals. The glove was equipped with flex sensors to make it possible to control a robotic hand and a hand in virtual reality (VR). In psychophysical experiments, human participants were able to discern combinations of electrotactile, vibrotactile, and thermal stimulation in VR. Participants trained to associate these sensations with roughness, hardness, and temperature had an overall accuracy of 98%, while untrained participants had an accuracy of 85%. Sensations could similarly be conveyed using a robotic hand equipped with sensors for pressure and temperature.

Exploring the limits of sensitivity for strain gauges of graphene and hexagonal boron nitride decorated with metallic nanoislands.

The purpose of this work is to clarify the mechanism of piezoresistance in a class of ultra-sensitive strain gauges based on metallic films on 2D substrates ("2D/M" films). The metals used are gold or palladium deposited as ultrathin films (≤16 nm). These films transition from a regime of subcontiguous growth to a percolated morphology with increasing nominal thickness. The 2D substrates are either single-layer graphene or hexagonal boron nitride (hBN). By using either a conductor (graphene) or an insulator (hBN), it is possible to de-couple the relative contributions of the metal and the 2D substrate from the overall piezoresistance of the composite structure. Here, we use a combination of measurements including electron microscopy, automated image analysis, temperature-dependent conductivity, and measurements of gauge factor of the films as they are bent over a 1 µm step edge (0.0001% or 1 ppm). Our observations are enumerated as follows: (1) of the four permutations of metal and 2D substrate, all combinations except hBN/Au are able to resolve 1 ppm strain (considered extraordinary for strain gauges) at some threshold thickness of metal; (2) for non-contiguous (i.e., unpercolated) films of metal on hBN, changes in resistance for these small step strains cannot be detected; (3) for percolated films on hBN, changes in resistance upon strain can be resolved only for palladium and not for gold; (4) graphene does not exhibit detectable changes in resistance when subjected to step strains of either 1 or 10 ppm, but does so upon the deposition of any amount of gold or palladium, even for nominal thicknesses below the threshold for percolation. Our observations reveal unexpected complexity in the properties of these simple composite materials, and ways in which these materials might be combined to exhibit even greater sensitivity.

Video for Active and Remote Learning.

The outbreak of COVID-19 has caused the canceling of in-person lectures on a massive scale. Rapid movement of education to online platforms will eventually lead to innovations in remote education. At the moment, however, instructors lack guidance. This short article describes approaches for producing video for remote and active learning.

Organic Haptics: Intersection of Materials Chemistry and Tactile Perception.

The goal of the field of haptics is to create technologies that manipulate the sense of touch. In virtual and augmented reality, haptic devices are for touch what loudspeakers and RGB displays are for hearing and vision. Haptic systems that utilize micromotors or other miniaturized mechanical devices (e.g., for vibration and pneumatic actuation) produce interesting effects, but are quite far from reproducing the feeling of real materials. They are especially deficient in recapitulating surface properties: fine texture, friction, viscoelasticity, tack, and softness. The central argument of this Progress Report is that to reproduce the feel of everyday objects requires chemistry: molecular control over the properties of materials and ultimately design of materials which can change these properties in real time. Stimuli-responsive organic materials, such as polymers and composites, are a class of materials which can change their oxidation state, conductivity, shape, and rheological properties, and thus might be useful in future haptic technologies. Moreover, the use of such materials in research on tactile perception could help elucidate the limits of human tactile sensitivity. The work described represents the beginnings of this new area of inquiry, in which the defining approach is the marriage of materials science and psychology.