Gait Pattern Analysis: Integration of a Highly Sensitive Flexible Pressure Sensor on a Wireless Instrumented Insole.

Gait phase monitoring wearable sensors play a crucial role in assessing both health and athletic performance, offering valuable insights into an individual's gait pattern. In this study, we introduced a simple and cost-effective capacitive gait sensor manufacturing approach, utilizing a micropatterned polydimethylsiloxane dielectric layer placed between screen-printed silver electrodes. The sensor demonstrated inherent stretchability and durability, even when the electrode was bent at a 45-degree angle, it maintained an electrode resistance of approximately 3 Ω. This feature is particularly advantageous for gait monitoring applications. Furthermore, the fabricated flexible capacitive pressure sensor exhibited higher sensitivity and linearity at both low and high pressure and displayed very good stability. Notably, the sensors demonstrated rapid response and recovery times for both under low and high pressure. To further explore the capabilities of these new sensors, they were successfully tested as insole-type pressure sensors for real-time gait signal monitoring. The sensors displayed a well-balanced combination of sensitivity and response time, making them well-suited for gait analysis. Beyond gait analysis, the proposed sensor holds the potential for a wide range of applications within biomedical, sports, and commercial systems where soft and conformable sensors are preferred.

Supramolecular complexation of C60 with branched polyethylene.

Fullerene C60 is a ubiquitous material for application in organic electronics and nanotechnology, due to its desirable optoelectronic properties including good molecular orbital alignment with electron-rich donor materials, as well as high and isotropic charge carrier mobility. However, C60 possesses two limitations that hinder its integration into large-scale devices: (1) poor solubility in common organic solvents leading to expensive device processing, and (2) poor optical absorbance in the visible portion of the spectrum. Covalent functionalization has long been the standard for introducing structural tunability into molecular design, but non-covalent interactions have emerged as an alternative strategy to tailor C60-based materials, offering a versatile and tuneable alternative to novel functional materials and applications. In this work, we report a straightforward non-covalent functionalization of C60 with a branched polyethylene (BPE), which occurs spontaneously in dilute chloroform solution under ambient conditions. A detailed characterization strategy, based on UV-vis spectroscopy and size-exclusion chromatography was performed to verify and investigate the structure of the C60+BPE complex. Among others, our work reveals that the supramolecular complex has an order of magnitude higher molecular weight than its C60 and BPE constituents and points towards oxidation as the driving force behind complexation. The C60+BPE complex also possesses significantly broadened optical absorbance compared to unfunctionalized C60, extending further into the visible portion of the spectrum. This non-covalent approach presents an inexpensive route to address the shortcomings of C60 for electronic applications, situating the C60+BPE complex as a promising candidate for further investigation in organic electronic devices.

Real-time correlation of crystallization and segmental order in conjugated polymers.

Modulating the segmental order in the morphology of conjugated polymers is widely recognized as a crucial factor for achieving optimal electronic properties and mechanical deformability. However, it is worth noting that the segmental order is typically associated with the crystallization process, which can result in rigid and brittle long-range ordered crystalline domains. To precisely control the morphology, a comprehensive understanding of how highly anisotropic conjugated polymers form segmentally ordered structures with ongoing crystallization is essential, yet currently elusive. To fill this knowledge gap, we developed a novel approach with a combination of stage-type fast scanning calorimetry and micro-Raman spectroscopy to capture the series of specimens with a continuum in the polymer percent crystallinity and detect the segmental order in real-time. Through the investigation of conjugated polymers with different backbones and side-chain structures, we observed a generally existing phenomenon that the degree of segmental order saturates before the maximum crystallinity is achieved. This disparity allows the conjugated polymers to achieve good charge carrier mobility while retaining good segmental dynamic mobility through the tailored treatment. Moreover, the crystallization temperature to obtain optimal segmental order can be predicted based on Tg and Tm of conjugated polymers. This in-depth characterization study provides fundamental insights into the evolution of segmental order during crystallization, which can aid in designing and controlling the optoelectronic and mechanical properties of conjugated polymers.

Human-Robot Interaction Using Learning from Demonstrations and a Wearable Glove with Multiple Sensors.

Human-robot interaction is of the utmost importance as it enables seamless collaboration and communication between humans and robots, leading to enhanced productivity and efficiency. It involves gathering data from humans, transmitting the data to a robot for execution, and providing feedback to the human. To perform complex tasks, such as robotic grasping and manipulation, which require both human intelligence and robotic capabilities, effective interaction modes are required. To address this issue, we use a wearable glove to collect relevant data from a human demonstrator for improved human-robot interaction. Accelerometer, pressure, and flexi sensors were embedded in the wearable glove to measure motion and force information for handling objects of different sizes, materials, and conditions. A machine learning algorithm is proposed to recognize grasp orientation and position, based on the multi-sensor fusion method.

Facile Blending Strategy for Boosting the Conjugated Polymer Semiconductor Transistor's Mobility.

The optimization of field-effect mobility in polymer field-effect transistors (FETs) is a critical parameter for advancing organic electronics. Today, many challenges still persist in understanding the roles of the design and processing of semiconducting polymers toward electronic performance. To address this, a facile approach to solution processing using blends of PDPP-TVT and PTPA-3CN is developed, resulting in a 3.5-fold increase in hole mobility and retained stability in electrical performance over 3 cm2 V-1 s-1 after 20 weeks. The amorphous D-A conjugated structure and strong intramolecular polarity of PTPA-3CN are identified as major contributors to the observed improvements in mobility. Additionally, the composite analysis by X-ray photoelectron spectroscopy (XPS) and the flash differential scanning calorimetry (DSC) technique showed a uniform distribution and was well mixed in binary polymer systems. This mobility enhancement technique has also been successfully applied to other polymer semiconductor systems, offering a new design strategy for blending-type organic transistor systems. This blending methodology holds great promise for the practical applications of OFETs.

An Azomethine-H-Based Fluorogenic Sensor for Formic Acid.

Formic acid (FA) is an important C1-containing feedstock that serves as a masked source of dihydrogen gas (H2). To encourage the adoption of cleaner (noncarbonaceous) energy sources, FA detection and sensing is thus of considerable interest. Here, we examine the use of a commercially available dye, azomethine-H (Az-H), for FA sensing. Solution studies confirm that FA quenches both the absorbance and the luminescence properties of Az-H. FA was additionally found to attenuate a known Az-H (E)-to-(Z) conformational change, suggesting an Az-H/FA interaction, possibly through hydrogen bonding; this phenomenon was probed using 1H NMR spectroscopy. Moving toward a solid-state sensor, the Az-H probe was incorporated into a gelatin-based matrix. On exposure to FA, the luminescence of this system was found to increase in a FA-dependent manner, attributed to the formation of stable hydrogen-bonded structures, facilitating a (Z)-to-(E) isomerization via imine protonation, allowing for production of the more luminescent (E)-isomer. This fluorogenic signal was used as a FA sensor with an estimated detection limit of ca. 0.4 ppb FA vapor. This work constitutes an important step toward a highly sensitive FA sensor in both the solution and solid state, opening new space for the detection of organic acids in differing chemical environments.

Graphene Inks Printed by Aerosol Jet for Sensing Applications: The Role of Dispersant on the Inks' Formulation and Performance.

This study presents graphene inks produced through the liquid-phase exfoliation of graphene flakes in water using optimized concentrations of dispersants (gelatin, triton X-100, and tween-20). The study explores and compares the effectiveness of the three different dispersants in creating stable and conductive inks. These inks can be printed onto polyethylene terephthalate (PET) substrates using an aerosol jet printer. The investigation aims to identify the most suitable dispersant to formulate a high-quality graphene ink for potential applications in printed electronics, particularly in developing chemiresistive sensors for IoT applications. Our findings indicate that triton X-100 is the most effective dispersant for formulating graphene ink (GTr), which demonstrated electrical conductivity (4.5 S·cm-1), a high nanofiller concentration of graphene flakes (12.2%) with a size smaller than 200 nm (<200 nm), a low dispersant-to-graphene ratio (5%), good quality as measured by Raman spectroscopy (ID/IG ≈ 0.27), and good wettability (θ ≈ 42°) over PET. The GTr's ecological benefits, combined with its excellent printability and good conductivity, make it an ideal candidate for manufacturing chemiresistive sensors that can be used for Internet of Things (IoT) healthcare and environmental applications.

Gels of Semiconducting Polymers in Benign Solvents.

Gels of semiconducting polymers have many potential applications, including biomedical devices and sensors. Here, we report a self-assembled gel system consisting of isoindigo-based semiconducting polymers with galactose side chains in benign, alcohol-based solvents. Because of the carbohydrate side chains, the modified isoindigo polymers are soluble in alcohols. We obtained thermoreversible gels in 1-propanol using these polymers and di-Fmoc-l-lysine, a molecular gelator. The polymers and molecular gelators have been selected in such a way that they do not have significant physical interactions. The molecular gelator self-assembled to form a fibrous structure that confines the polymer chains in the interstitial spaces of the fibers. The polymer chains formed local aggregations and increased the shear moduli of the gels significantly. Bulky galactose side chains and the less planar nature of the polymer backbone hindered the formation of long-range assembled structures of the polymers. However, the dispersion of polymers throughout the gel samples resulted in a percolated structure in the dried gel films. The bulk electrical conductivity of dried gels confirmed the presence of such percolated structures. Our results demonstrated that carbohydrate-containing conjugated polymers can be combined with molecular gelators to obtain gels in eco-friendly solvents.

Molecular Structure and Conformational Design of Donor-Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property.

Tuning the optoelectronic properties of donor-acceptor conjugated polymers (D-A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D-A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D-A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D-A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.

Conjugated Polymer Nanoparticles as a Universal High-Affinity Probe for the Selective Detection of Microplastics.

Microplastic (MP) pollution is a global challenge that requires immediate mitigation practices. Monitoring is crucial for quantifying MPs, but their mitigation remains very challenging due to several factors, including the lack of selective materials to specific polymers, and the low sensitivity of the current detection techniques. In this work, we introduce a novel design for the selective detection of MPs through fluorescence spectroscopy by exploiting conjugated polymer nanoparticles (CPNs). Fluorescent diketopyrrolopyrrole nanoparticles were prepared by nanoprecipitation to incorporate peripheral hyaluronic acid to increase their affinity for various plastics. The affinity of the new ligand for various types of MPs was examined through several characterization techniques, including fluorescence spectroscopy and microscopy, nanoparticle tracking analysis and computational studies. The new CPN were shown to be highly fluorescent in the presence of typically abundant MPs, achieving very strong binding constants in the picomolar range. This very strong affinity for a broad family of plastics was found to be the results of cooperative supramolecular effects and topographical affinity, as probed by advanced microscopy and in silico studies. Furthermore, the new affinity probes were shown to be highly selective for MPs, allowing for their detection in heterogeneous samples, including soil debris and other organic contaminants. The new materials design introduced in this work constitute a promising platform for the development of novel MP detection devices directly useable at the point of collection. Moreover, it opens new avenue for the mitigation of this environmental hazard through tailorable materials.

Amide-Assisted Polymerization of 1,3-Butadiyne Containing Thiolate Ligands on Small Gold Nanoparticles.

Incorporation of directing amide groups has been shown to facilitate the topochemical polymerization of 1,3-butadiyne (diacetylene) groups in noncrystalline phases such as gels, amorphous solids, and liquid crystals. It remains challenging to polymerize 1,3-butadiyne-containing alkylthiolate ligands within their self-assembled monolayers on gold nanoparticles (AuNPs), which enhances their stability and adds new optical and electronic properties. Especially smaller AuNPs of sizes below 5 nm in diameter have been reported to display sluggish photopolymerization and are susceptible to photodegradation under UV irradiation. To probe the effectiveness of the amide-directed photopolymerization of 1,3-butadiyne ligands, small AuNPs in the 2-4 nm range were synthesized that contain alkylthiolate ligands with and without amide and 1,3-butadiyne groups. Their photopolymerization and photostability were studied by transmission electron microscopy (TEM), UV-vis spectroscopy, and Raman spectroscopy. AuNP with amide-free 1,3-butadiyne ligands templated the polymerization of the 1,3-butadiyne ligands but fused to large and insoluble particles during the polymerization process. AuNPs with ligands containing both 1,3-butadiyne and amide groups polymerized significantly faster, which slowed down photodegradation. A UV irradiation (254 nm and 176 W/m2) for 5-10 min was found to be optimal for the AuNPs with directing amide groups studied here, although their average core sizes grew from 3.8 to 4.0 nm in diameter and about 20% of the attached 1,3-butadiyne ligands remained unreacted after 10 minutes of irradiation. About 75% of the attached 1,3-butadiyne ligands were already polymerized during the first 5 min of UV irradiation. This decrease in reactivity is reasoned with a fast polymerization of ligands attached to facet sites and slower polymerization rates for ligands attached to edge and corner sites. Unexpectedly, photopolymerization occurred only in the presence of solvent, whereas no polydiacetylene was generated when dry powders of any of the diacetylene-containing gold nanoparticles were irradiated.

Impairing proliferation of glioblastoma multiforme with CD44+ selective conjugated polymer nanoparticles.

Glioblastoma is one of the most aggressive types of cancer with success of therapy being hampered by the existence of treatment resistant populations of stem-like Tumour Initiating Cells (TICs) and poor blood-brain barrier drug penetration. Therapies capable of effectively targeting the TIC population are in high demand. Here, we synthesize spherical diketopyrrolopyrrole-based Conjugated Polymer Nanoparticles (CPNs) with an average diameter of 109 nm. CPNs were designed to include fluorescein-conjugated Hyaluronic Acid (HA), a ligand for the CD44 receptor present on one population of TICs. We demonstrate blood-brain barrier permeability of this system and concentration and cell cycle phase-dependent selective uptake of HA-CPNs in CD44 positive GBM-patient derived cultures. Interestingly, we found that uptake alone regulated the levels and signaling activity of the CD44 receptor, decreasing stemness, invasive properties and proliferation of the CD44-TIC populations in vitro and in a patient-derived xenograft zebrafish model. This work proposes a novel, CPN- based, and surface moiety-driven selective way of targeting of TIC populations in brain cancer.

Ferrocene metallopolymers of intrinsic microporosity (MPIMs).

We show here that non-network metallopolymers can possess intrinsic microporosity stemming from contortion introduced by metallocene building blocks. Metallopolymers constructed from ferrocenyl building blocks linked by phenyldiacetylene bridges are synthesized and possess BET surface areas up to 400 m2 g-1. As solubility imparted by pendant groups reduces porosity, copolymerization is used to simultaneously improve both accessible surface area and solubility. Spectroscopic analysis provides evidence that mixed valency between neighboring ferrocenyl units is supported in these polymers.

Modulating the Photophysical Properties and Electron Transfer Rates in Diketopyrrolopyrrole-Based Coordination Polymers.

Molecular self-assembly through noncovalent interactions is a particularly efficient approach to fine-tune the optoelectronic and photophysical properties of electroactive materials. In metal-ligand coordination polymers, the final properties of the assemblies are directly related to the nature of the metal-ligand interaction. To probe for such influence on the photophysical properties of electroactive materials, a series of coordination polymers based on a well-known organic dye, diketopyrrolopyrrole, was prepared through coordination of a terpyridine-containing monomer with various metal sources, including iron, cobalt, zinc, and manganese. The resulting supramolecular polymers were characterized through multiple techniques, including UV-vis and fluorescence spectroscopy, time-correlated single-photon counting, and femtosecond transient absorption spectroscopy to reveal the impact of the metal source on the final photophysical properties of coordination polymers. As expected, important variations were found between different coordination polymers in terms of absorption, fluorescence kinetics, and electron transfer rate. While iron and cobalt-containing polymers showed ultrafast electrons transfer rates, assemblies from manganese were shown to be much less efficient, confirming the importance of metal centers. This detailed fundamental study unravels some important relationships between metal-ligand interactions, supramolecular self-assembly, and photophysical properties, ultimately leading to new avenues for the design of functional polymers based on organic dyes.

Enhancing the Solubility of Semiconducting Polymers in Eco-Friendly Solvents with Carbohydrate-Containing Side Chains.

Semiconducting polymers are at the forefront of next-generation organic electronics due to their robust mechanical and optoelectronic properties. However, their extended π-conjugation often leads to materials with low solubilities in common organic solvents, thus requiring processing in high-boiling-point and toxic halogenated solvents to generate thin-film devices. To address this environmental concern, a natural product-inspired side-chain engineering approach was used to incorporate galactose-containing moieties into semiconducting polymers toward improved processability in greener solvents. Novel isoindigo-based polymers with different ratios of galactose-containing side chains were synthesized to improve the solubilities of the organic semiconductors in alcohol-based solvents. The addition of carbohydrate-containing side chains to π-conjugated polymers was found to considerably impact the intermolecular aggregation of the materials and their microstructures in the solid state as confirmed by atomic force microscopy and grazing-incidence wide-angle X-ray scattering. The charge transport characteristics of the new semiconductors were evaluated by the fabrication of organic field-effect transistors prepared from both toxic halogenated and greener alcohol-based solvents. Importantly, the incorporation of carbohydrate-containing side chains was shown to have very little detrimental impact on the electronic properties of the polymer when processed from green solvents.

SMART transfer method to directly compare the mechanical response of water-supported and free-standing ultrathin polymeric films.

Intrinsic mechanical properties of sub-100 nm thin films are markedly difficult to obtain, yet an ever-growing necessity for emerging fields such as soft organic electronics. To complicate matters, the interfacial contribution plays a major role in such thin films and is often unexplored despite supporting substrates being a main component in current metrologies. Here we present the shear motion assisted robust transfer technique for fabricating free-standing sub-100 nm films and measuring their inherent structural-mechanical properties. We compare these results to water-supported measurements, exploring two phenomena: 1) The influence of confinement on mechanics and 2) the role of water on the mechanical properties of hydrophobic films. Upon confinement, polystyrene films exhibit increased strain at failure, and reduced yield stress, while modulus is reduced only for the thinnest 19 nm film. Water measurements demonstrate subtle differences in mechanics which we elucidate using quartz crystal microbalance and neutron reflectometry.

The biosynthesis of the cannabinoids.

Cannabis has been integral to Eurasian civilization for millennia, but a century of prohibition has limited investigation. With spreading legalization, science is pivoting to study the pharmacopeia of the cannabinoids, and a thorough understanding of their biosynthesis is required to engineer strains with specific cannabinoid profiles. This review surveys the biosynthesis and biochemistry of cannabinoids. The pathways and the enzymes' mechanisms of action are discussed as is the non-enzymatic decarboxylation of the cannabinoic acids. There are still many gaps in our knowledge about the biosynthesis of the cannabinoids, especially for the minor components, and this review highlights the tools and approaches that will be applied to generate an improved understanding and consequent access to these potentially biomedically-relevant materials.

Topochemical Polymerization of a Nematic Tetraazaporphyrin Derivative To Generate Soluble Polydiacetylene Nanowires.

Polydiacetylenes are well-established one-dimensional organic semiconductors that have been generated by photochemical and thermal polymerizations of diacetylenes in single crystals, gel phases, thin films, and membranes. Their formation in mesophases, such as liquid crystals, has been surprisingly little studied although higher-ordered mesophases should support the topochemical polymerization of diacetylenes (1,3-butadiyne groups) and may give access to large domains of uniformly aligned materials. The polymerization of diacetylenes in a mesophase may also increase the stability of the self-assembled supramolecular structure. Here, the dye and discotic mesogen tetraazaporphyrin was decorated with eight diacetylene-containing alkyl chains to probe its mesomorphism and conversion into multifunctional polydiacetylene materials. While the incorporation of diacetylene groups supports columnar mesomorphism, successful photopolymerization required the presence of directing amide groups that suppressed columnar in favor of nematic mesomorphism. Still, the polymerization of the nematic mesophase generated a soluble nematic polydiacetylene of significantly higher molecular weight (Mn = 77 kDa or 25 monomer units by gel permeation chromatography) than what has been obtained in gel phases of related compounds. The formation of polydiacetylene was confirmed by Raman spectroscopy, and its nematic structure was verified by UV-vis spectroscopy, polarized optical microscopy, and X-ray diffraction. Both its nematic structure and the incorporation of eight side chains per discotic unit provide the polydiacetylene with sufficient solubility for casting thin films on substrates. Atomic force microscopy studies of films on silicon wafers revealed a grid-like structure of connected nanofibers. This study demonstrates the requirements for the formation of multifunctional mesomorphic polydiacetylene materials from mesomorphic precursors and their advantages. Optimization of the presented molecular design should give access to other mesophases and, consequently, functional polydiacetylene materials with tunable structures and optoelectronic properties.

Imine and metal-ligand dynamic bonds in soft polymers for autonomous self-healing capacitive-based pressure sensors.

In this work, a facile and simple yet effective method to generate intrinsic autonomous self-healing polymers was developed, leading to new materials that can be easily fine-tuned both mechanically and chemically. The new materials were designed to incorporate two dynamic and reversible types of chemical bonds, namely dynamic imine and metal-coordinating bonds, to enable autonomous self-healing, controlled degradability and ultra-high tunable stretchability (up to 800% strain) based on the ratio of metal to ligand incorporated. Through an easy condensation reaction, imine bonds are generated at the end-termini of a short siloxane chain. The new dynamic system was characterized by a variety of techniques, including tensile-pull strain testing, atomic force microscopy and UV-Vis spectroscopy, which showed that the highly dynamic imine bonds, combined with coordination with Fe2+ ions, allow for the material to regenerate 88% of its mechanical strength after physical damage. The materials were also controlled to be degraded in mild acidic conditions. Lastly, application in self-healable electronics was demonstrated through the fabrication of a capacitive-based pressure sensor, which shows good sensitivity and dynamic response (∼0.33 kPa-1) before and after healing.

Morphology and Electronic Properties of Semiconducting Polymer and Branched Polyethylene Blends.

A new strategy for influencing the solid-state morphology of conjugated polymers was developed through physical blending with a low-molecular-weight branched polyethylene. This nontoxic and low-boiling-point additive was blended with a high-charge-mobility diketopyrrolopyrrole-based conjugated polymer, and a detailed investigation of the new blended materials was performed by various characterization tools, including X-ray diffraction, UV-vis spectroscopy, and atomic force microscopy. Interestingly, the branched additive was shown to reduce the crystallinity of the conjugated polymer while promoting aggregation and phase separation in the solid state. Upon thermal removal of the olefinic additive, the thin films maintained a lower crystallinity and aggregated morphology in comparison to a nonblended polymer. The semiconducting performance of the new branched polyethylene/conjugated polymer blends was also investigated in organic field-effect transistors, which showed a stable charge mobility of around 0.3 cm2 V-1 s-1 without thermal annealing, independent of the blending ratio. Furthermore, using the new polyethylene-based additive, the concentration of a conjugated polymer required for the fabrication of organic field-effect transistor devices was reduced down to 0.05 wt %, without affecting charge transport, which represents a significant improvement compared to usual concentrations used for solution deposition. Our results demonstrate that the physical blending of a conjugated polymer with nontoxic, low-molecular-weight branched polyethylene is a promising strategy for the modification and fine-tuning of the solid-state morphology of conjugated polymers without sacrificing their charge-transport properties, thus creating new opportunities for the large-scale processing of organic semiconductors.