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Flexible electronics have gained more attention for emerging electronic devices such as sensors, biosensors, and batteries with advantageous properties including being thin, lightweight, flexible, and low-cost. The development of various forms of allotropic carbon papers provided a new dry-manufacturing route for the fabrication of flexible and wearable electronics, while the electrochemical performance and the bending stability are largely influenced by the bulk morphology and the micro-/nanostructured domains of the carbon papers. Here, we evaluate systematically the intrinsic physicoelectrochemical properties of allotropic carbon-based conducting papers as flexible electrodes including carbon-nanotubes-paper (CNTs-paper), graphene-paper (GR-paper), and carbon-fiber-paper (CF-paper), followed by functionalization of the allotropic carbon papers for the fabrication of flexible electrodes. The morphology, chemical structure, and defects originating from the allotropic nanostructured carbon materials were characterized by scanning electron microscopy (SEM) and Raman spectroscopy, followed by evaluating the electrochemical performance of the corresponding flexible electrodes by cyclic voltammetry and electrochemical impedance spectroscopy. The electron-transfer rate constants of the CNTs-paper and GR-paper electrodes were ∼14 times higher compared with the CF-paper electrode. The CNTs-paper and GR-paper electrodes composed of nanostructured carbon showed significantly higher bending stabilities of 5.61 and 4.96 times compared with the CF-paper. The carbon-paper flexible electrodes were further functionalized with an inorganic catalyst, Prussian blue (PB), forming the PB-carbon-paper catalytic electrode and an organic conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), forming the PEDOT-carbon-paper capacitive electrode. The intrinsic attribute of different allotropic carbon electrodes affects the deposition of PB and PEDOT, leading to different electrocatalytic and capacitive performances. These findings are insightful for the future development and fabrication of advanced flexible electronics with allotropic carbon papers.

Extracellular matrix (ECM) components govern a range of cell functions, such as migration, proliferation, maintenance of stemness, and differentiation. Cell niches that harbor stem‐/progenitor cells, with matching ECM, have been shown in a range of organs, although their presence in the heart is still under debate. Determining niches depends on a range of in vitro and in vivo models and techniques, where animal models are powerful tools for studying cell‐ECM dynamics; however, they are costly and time‐consuming to use. In vitro models based on recombinant ECM proteins lack the complexity of the in vivo ECM. To address these issues, we present the spatiotemporal extracellular matrix model for studies of cell‐ECM dynamics, such as cell niches. This model combines gentle decellularization and sectioning of cardiac tissue, allowing retention of a complex ECM, with recellularization and subsequent image processing using image stitching, segmentation, automatic binning, and generation of cluster maps. We have thereby developed an in situ representation of the cardiac ECM that is useful for assessment of repopulation dynamics and to study the effect of local ECM composition on phenotype preservation of reseeded mesenchymal progenitor cells. This model provides a platform for studies of organ‐specific cell‐ECM dynamics and identification of potential cell niches. Spatiotemporal extracellular matrix modeling facilitates the identification of cell‐niches by combining decellularized whole organ sections and recellularization with a new algorithm for automatic generation of density maps and cluster‐analysis for identification of regions of interest.

Modulation of chemical functional groups on conducting polymers (CPs) provides an effective way to tailor the physicochemical properties and electrochemical performance of CPs, as well as serves as a functional interface for stable integration of CPs with biomolecules for organic bioelectronics (OBEs). Herein, we introduced a facile approach to modulate the carboxylate functional groups on the PEDOT interface through a systematic evaluation on the effect of a series of carboxylate-containing molecules as counterion dopant integrated into the PEDOT backbone, including acetate as monocarboxylate (mono-COO–), malate as dicarboxylate (di-COO–), citrate as tricarboxylate (tri-COO–), and poly(acrylamide-co-acrylate) as polycarboxylate (poly-COO–) bearing different amounts of molecular carboxylate moieties to create tunable PEDOT:COO–interfaces with improved polymerization efficiency. We demonstrated the modulation of PEDOT:COO–interfaces with various granulated morphologies from 0.33 to 0.11 μm, tunable surface carboxylate densities from 0.56 to 3.6 μM cm–2, and with improved electrochemical kinetics and cycling stability. We further demonstrated the effective and stable coupling of an enzyme model lactate dehydrogenase (LDH) with the optimized PEDOT:poly-COO–interface via simple covalent chemistry to develop biofunctionalized PEDOT (Bio-PEDOT) as a lactate biosensor. The biosensing mechanism is driven by a sequential bioelectrochemical signal transduction between the bio-organic LDH and organic PEDOT toward the concept of all-polymer-based OBEs with a high sensitivity of 8.38 μA mM–1cm–2and good reproducibility. Moreover, we utilized the LDH-PEDOT biosensor for the detection of lactate in spiked serum samples with a high recovery value of 91–96% and relatively small RSD in the range of 2.1–3.1%. Our findings provide a new insight into the design and optimization of functional CPs, leading to the development of new OBEs for sensing, biosensing, bioengineering, and biofuel cell applications.

The rapidly developing field of conducting polymers in organic electronics has many implications for bioelectronics. For biosensing applications, tailoring the functionalities of the conducting polymer’s surface is an efficient approach to improve both sensitivity and selectivity. Here, we demonstrated a facile and economic approach for the fabrication of a high-density, negatively charged carboxylic-acid-group-functionalized PEDOT (PEDOT:COOH) using an inexpensive ternary carboxylic acid, citrate, as a dopant. The polymerization efficiency was significantly improved by the addition of LiClO4as a supporting electrolyte yielding a dense PEDOT:COOH sensing interface. The resulting PEDOT:COOH interface had a high surface density of carboxylic acid groups of 0.129 μmol/cm2as quantified by the toluidine blue O (TBO) staining technique. The dopamine response measured with the PEDOT:COOH sensing interface was characterized by cyclic voltammetry with a significantly reduced ΔEpof 90 mV and a 3-fold increase in the Ipavalue compared with those of the nonfunctionalized PEDOT sensing interface. Moreover, the cyclic voltammetry and electrochemical impedance spectroscopy results demonstrated the increased electrode kinetics and highly selective discrimination of dopamine (DA) in the presence of the interferents ascorbic acid (AA) and uric acid (UA), which resulted from the introduction of negatively charged carboxylic acid groups. The negatively charged carboxylic acid groups could favor the transfer, preconcentration, and permeation of positively charged DA to deliver improved sensing performance while repelling the negatively charged AA and UA interferents. The PEDOT:COOH interface facilitated measurement of dopamine over the range of 1–85 μM, with a sensitivity of 0.228 μA μM–1, which is 4.1 times higher than that of a nonfunctionalized PEDOT electrode (0.055 μA μM–1). Our results demonstrate the feasibility of a simple and economic fabrication of a high-density PEDOT:COOH interface for chemical sensing, which also has the potential for coupling with other biorecognition molecules via carboxylic acid moieties for the development of a range of advanced PEDOT-based biosensors.

Microparticles have attracted much attention for medical, analytical and biological applications. Calcium carbonate (CaCO3) templating method with the advantages of having narrow size distribution, controlled morphology and good biocompatibility that has been widely used for the synthesis of various protein-based microparticles. Despite CaCO3template is biocompatible, most of the conventional methods to create stable protein microparticles are mainly driven by chemical crosslink reagents which may induce potential harmful effect and remains undesirable especially for biomedical or clinical applications. In this article, we demonstrate the fabrication of protein microparticles and microcapsules with an innovative method using biomolecular tools such as enzymes and affinity molecules to trigger the assembling of protein molecules within a porous CaCO3template followed by a template removal step. We demonstrated the enzyme-assisted fabrication of collagen microparticles triggered by transglutaminase, as well as the affinity-assisted fabrication of BSA-biotin avidin microcapsules triggered by biotin-avidin affinity interaction, respectively. Based on the different protein assemble mechanisms, the collagen microparticles appeared as a solid-structured particles, while the BSA-biotin avidin microcapsules appeared as hollow-structured morphology. The fabrication procedures are simple and robust that allows producing protein microparticles or microcapsules under mild conditions at physiological pH and temperature. In addition, the microparticle morphologies, protein compositions and the assemble mechanisms were studied. Our technology provides a facile approach to design and fabricate protein microparticles and microcapsules that are useful in the area of biomaterials, pharmaceuticals and analytical chemistry.

Printable organic bioelectronics provide a fast and cost-effective approach for the fabrication of novel biodevices, while the general challenge is to achieve optimized reaction kinetics at multiphase boundaries between biomolecules and electrodes. Here, we present an entirely new concept based on a modular approach for the construction of heterostructured bioelectronic interfaces by using tailored functional “biological microparticles” combined with “transducer microparticles” as modular building blocks. This approach offers high versatility for the design and fabrication of bioelectrodes with a variety of forms of interparticle spatial organization, from layered-structures to more advance bulk heterostructured architectures. The heterostructured biocatalytic electrodes delivered twice the reaction rate and a six-fold increase in the effective diffusion kinetics in response to a catalytic model using glucose as the substrate, together with the advantage of shortened diffusion paths for reactants between multiple interparticle junctions and large active particle surface. The consequent benefits of this improved performance combined with the simple means of mass production are of major significance for the emerging printed electronics industry.

There is increased usage of flexible electronics recently in various applications such as wearable devices, flexible displays and sensors. Studies on the durability of conductive metal traces under cyclic mechanical loading is crucial since these conductors will be subjected to repeated bending. In this work, the mechanical and electrical behavior of silver printed conductors was tested using cyclic three-point bend test. The samples were flexible polymer thick film (PTF) silver (Ag) ink printed on a flexible polyethylene terephthalate (PET) substrate. The durability of this PTF Ag ink, which has a hyper-elastic binder and Ag flakes, was studied by performing cyclic bending tests. Four-point resistivity measurements and imaging of the sample both before and after bending were performed. A custom tester machine was used to apply strain to the circuit and measure the resistivity of the silver trace. The results of the bending test show that the silver trace does not undergo significant deformation and the change in resistance is less than 0.6% under both tensile and compressive tests. Fatigue tests were also performed by cyclic bending tests for three trials in which batches of 10,000 cycles were completed. The printed silver wire withstood 30,000 cycles of bend tests and produced only 2.64% change in resistance. This indicates that the printed wires are very durable even after 30,000 cycles of outer bending. Imaging was also conducted on these samples to study the effect of repeated bending on the morphology of the silver conductive trace. Although there was an increase in surface roughness before and after cyclic bending, there was no obvious deformation or delamination observed in the samples.

We have demonstrated an entirely new concept of a wearable theranostic device in the form of a contact lens (theranostic lens) with a dual-functional hybrid surface to modulate and detect a pathogenic attack, using a the corneal HSV serotype-1 (HSV-1) model. The theranostic lenses were constructed using a facile layer-by-layer surface engineering technique, keeping the theranostic lenses with good surface wettability, optically transparency, and nontoxic toward human corneal epithelial cells. The theranostic lenses were used to capture and concentrate inflammatory cytokines such as interleukin-1α (IL-1α), which is upregulated during HSV-1 reactivation, for sensitive, noninvasive diagnostics. The theranostic lens also incorporated an antiviral coating to serve as a first line of defense to protect patients against disease. Our strategy tackles major problems in tear diagnostics that are mainly associated with the sampling of a relatively small volume of fluid and the low concentration of biomarkers. The theranostic lenses show effective anti-HSV-1 activity and good analytical performance for the detection of IL-1α, with a limit of detection of 1.43 pg mL–1and a wide linear range covering the clinically relevant region. This work offers a new paradigm for “wearable” noninvasive healthcare devices combining “diagnosis” and “protection” against disease, while supporting patient compliance. We believe that this approach holds immense promise as a next-generation point-of-care and decentralized diagnostic/theranostic platform for a range of biomarkers.

In this article, a non‐chemical crosslinking method is used to produce pure protein microparticles with an innovative approach, so‐called protein activation spontaneous and self‐assembly (PASS). The fabrication of protein microparticles is based on the idea of using the internal disulfide bridges within protein molecules as molecular linkers to assemble protein molecules into a microparticle form. The assembly process is triggered by an activating reagent–dithiothreitol (DTT), which only involved in the intermediate step without being incorporated into the resulting protein microparticles. Conventional protein microparticle fabrication methods usually involve emulsification process and chemical crosslink reactions using amine reactive reagents such as glutaraldehdye or EDC/NHS. The resulting protein microparticles are usually having various size distributions. Most importantly crosslinking reactions using amine reactive reagents will result in producing protein microparticles with undesired properties such as auto‐fluorescence and high toxicity. In contrast to the conventional methods, our technology provides a simple and robust method to produce highly homogeneous, stable and non‐fluorescence pure protein microparticles under mild conditions at physiological pH and temperature. The protein microparticles are found to be biodegradable, non‐toxic to MDCK cells and with preserved biological activities. Results on the cytotoxcity study and enzyme function demonstrate the potential applications of the protein microparticles in the area of pharmaceutics and analytical chemistry.

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Kodierung durch Verkapselung: Ein neuartiger Ansatz zur Herstellung von Polymerschalen kombiniert die Verkapselung von Biomolekülen mit der Kodierung der Kapseln. Gestreifte Polymerschalen, die durch nach innen gerichtete Diffusion von Poly(allylamin) in die Matrix von Agarose‐Mikrokugeln entstehen, dienen zur Verkapselung von Biomolekülen. Die Kodierung wird durch die Farb‐ und/oder Dickepermutation der gestreiften Polymerschalen erreicht (siehe Bild).

A novel approach to perform a high number of individual polymerase chain reactions (PCR) in microcapsule reaction compartments, termed “Microcapsule‐PCR” was developed. Temperature stable microcapsules with a selective permeable capsule wall were constructed by matrix‐assisted layer‐by‐layer (LbL) Encapsulation technique. During the PCR, small molecular weight building blocks – nucleotides (dNTPs) were supplied externally and diffuse through the permeable capsule wall into the interior, while the resulted high molecular weight PCR products were accumulated within the microcapsule. Microcapsules (∼110.8 µm average diameter) filled with a PCR reaction mixture were constructed by an emulsion technique having a 2% agarose core and a capsule formed by LbL coating with poly(allylamine‐hydrochloride) and poly(4‐styrene‐sulfonate). An encapsulation efficiency of 47% (measured for primer‐FITC (22 bases)) and 98% PCR efficiency was achieved. Microcapsules formed by eight layers of polyelectrolyte and subjected to PCR cycling (up to 95 °C) demonstrated good temperature stability without any significantly changes in DNA retention yield and microcapsule morphology. A multiplex Microcapsule‐PCR experiment demonstrated that microcapsules are individual compartment and do not exchange templates or primers between microcapsules during PCR cycling.

Flexible skin patch biosensors are promising for the noninvasive determination of physiological parameters in perspiration for fitness and health monitoring. However, various prerequisites need to be met for the development of such biosensors, including the creation of a flexible conductive platform, bending/contact stability, fast electrochemical kinetics, and immobilization of biomolecules. Here, we describe a conducting polymer-reinforced laser-irradiated graphene (LIG) network as a heterostructured three-dimensional (3D) transducer for flexible skin patch biosensors. LIG with a hierarchically interconnected graphene structure is geometrically patterned on polyimide via localized laser irradiation as a flexible conductive platform, which is then reinforced by poly(3,4-ethylenedioxythiophene) (PEDOT) as a conductive binder (PEDOT/LIG) with improved structural/contact stability and electrochemical kinetics. The interconnected pores of the reinforced PEDOT/LIG function as a 3D host matrix for high loading of “artificial” (Prussian blue, PB) and natural enzymes (lactate oxidase, LOx), forming a compact and heterostructured 3D transducer (LOx/PB-PEDOT/LIG) for lactate biosensing with excellent sensitivity (11.83 μA mM–1). We demonstrated the fabrication of flexible skin patch biosensors comprising a custom-built integrated three-electrode system achieve amperometric detection of lactate in artificial sweat over a wide physiological linear range of 0–18 mM. The advantage of this facile and versatile transducer is further illustrated by the development of a folded 3D wristband lactate biosensor and a dual channel biosensors for simultaneous monitoring of lactate and glucose. This innovative design concept of a heterostructured transducer for flexible biosensors combined with a versatile fabrication approach could potentially drive the development of new wearable and skin-mountable biosensors for monitoring various physiological parameters in biofluids for noninvasive fitness and health management.

The oxygen reduction reaction (ORR) is an essential process in electrocatalysis limiting the commercialization of sustainable energy conversion technologies, such as fuel cells. The use of conducting polymers as molecular porous and conducting catalysts obtained from the high abundance elements enables the route towards low cost and high-throughput fabrication of disposable plastic electrodes of fuel cells. Poly(3,4-ethylenedioxythiophene) (PEDOT) is a 2-electron ORR electrocatalyst yielding specifically hydrogen peroxide that limits the full utilization of chemical energy of oxygen. Here, we demonstrated an innovative product-to-intermediate relay approach achieving complete oxygen reduction reaction (cORR) with Prussian blue (PB) integrated microporous PEDOT cathode in fuel cells. The microporous structured PEDOT electrode prepared via a simple cryosynthesis allows the bulk integration and stabilization of the poor conducting PB co-catalyst into the PEDOT ion-electron conductor, while the microporous PEDOT allows effective oxygen diffusion into the matrix. We evaluated systematically the effect of sequential PEDOT 2-electron ORR followed by PB co-catalysis launching hydrogen peroxide reduction reaction (HPRR) into H2O. This resulted in the establishment of electronic and ionic transport between PEDOT and PB catalyst enabling the combination of enhanced ORR electrocatalysis by means of the ORR course extension from 2- to 4-electron reduction to achieve cORR. The cORR performance delivered by the product-to-intermediate relay between microporous PEDOT and PB co-catalysis led to a four times increase in power density of model proton-exchange membrane fuel cell (PEMFC) assembled from the polymer-based air-breathing cathode.