Toward Continuous Molecular Testing Using Gold-Coated Threads as Multi-Target Electrochemical Biosensors.

Analytical systems based on isothermal nucleic acid amplification tests (NAATs) paired with electroanalytical detection enable cost-effective, sensitive, and specific digital pathogen detection for various in situ applications such as point-of-care medical diagnostics, food safety monitoring, and environmental surveillance. Self-assembled monolayers (SAMs) on gold surfaces are reliable platforms for electroanalytical DNA biosensors. However, the lack of automation and scalability often limits traditional chip-based systems. To address these challenges, we propose a continuous thread-based device that enables multiple electrochemical readings on a functionalized working electrode Au thread with a single connection point. We demonstrate the possibility of rolling the thread on a spool, which enables easy manipulation in a roll-to-roll architecture for high-throughput applications. As a proof of concept, we have demonstrated the detection of recombinase polymerase amplification (RPA) isothermally amplified DNA from the two toxic microalgae species Ostreopsis cf. ovata and Ostreopsis cf. siamensis by performing a sandwich hybridization assay (SHA) with electrochemical readout.

A 3D paper microfluidic device for enzyme-linked assays: Application to DNA analysis.

A paper microfluidic device capable of conducting enzyme-linked assays is presented: a microfluidic enzyme-linked paper analytical device (µEL-PAD). The system exploits a wash-free sandwich coupling to form beads/analyte/enzyme complexes, which are subsequently added to the vertical flow device composed of wax-printed paper, waxed nitrocellulose membrane and absorbent/barrier layers. The nitrocellulose retains the bead complexes without disrupting the flow, enabling for an efficient washing step. The entrapped complexes then interact with the chromogenic substrate stored on the detection paper, generating a color change on it, quantified with an open-source smartphone software. This is a universal paper-based technology suitable for high-sensitivity quantification of many analytes, such as proteins or nucleic acids, with different enzyme-linked formats. Here, the potential of the µEL-PAD is demonstrated to detect DNA from Staphylococcus epidermidis. After generation of isothermally amplified genomic DNA from bacteria, Biotin/FITC-labeled products were analyzed with the µEL-PAD, exploiting streptavidin-coated beads and antiFITC-horseradish peroxidase. The µEL-PAD achieved a limit of detection (LOD) and quantification <10 genome copies/µL, these being at least 70- and 1000-fold lower, respectively, than a traditional lateral flow assay (LFA) exploiting immobilized streptavidin and antiFITC-gold nanoparticles. It is envisaged that the device will be a good option for low-cost, simple, quantitative, and sensitive paper-based point-of-care testing.

Portable electroanalytical nucleic acid amplification tests using printed circuit boards and open-source electronics.

The realization of electrochemical nucleic acid amplification tests (NAATs) at the point of care (POC) is highly desirable, but it remains a challenge given their high cost and lack of true portability/miniaturization. Here we show that mass-produced, industrial standardized, printed circuit boards (PCBs) can be repurposed to act as near-zero cost electrodes for self-assembled monolayer-based DNA biosensing, and further integration with a custom-designed and low-cost portable potentiostat. To show the analytical capability of this system, we developed a NAAT using isothermal recombinase polymerase amplification, bypassing the need of thermal cyclers, followed by an electrochemical readout relying on a sandwich hybridization assay. We used our sensor and device for analytical detection of the toxic microalgae Ostreopsis cf. ovata as a proof of concept. This work shows the potential of PCBs and open-source electronics to be used as powerful POC DNA biosensors at a low-cost.

Rapid prototyping of heterostructured organic microelectronics using wax printing, filtration, and transfer.

Conducting polymers are the natural choice for soft electronics. However, the main challenge is to pattern conducting polymers using a simple and rapid method to manufacture advanced devices. Filtration of conducting particle dispersions using a patterned membrane is a promising method. Here, we show the rapid prototyping of various micropatterned organic electronic heterostructures of PEDOT:PSS by inducing the formation of microscopic hydrogels, which are then filtered through membranes containing printed hydrophobic wax micropatterns. The hydrogels are retained on the un-patterned, hydrophilic regions, forming micropatterns, achieving a resolution reaching 100 µm. We further solve the problem of forming stacked devices by transferring the acidified PEDOT:PSS micropattern using the adhesive tape transfer method to form vertical heterostructures with other micropatterned electronic colloids such as CNTs, which are patterned using a similar technique. We demonstrate a number of different heterostructure devices including micro supercapacitors and organic electrochemical transistors and also demonstrate the use of acidified PEDOT:PSS microstructures in cell cultures to enable bioelectronics.

Nitrocellulose-bound achromopeptidase for point-of-care nucleic acid tests.

Enzymes are the cornerstone of modern biotechnology. Achromopeptidase (ACP) is a well-known enzyme that hydrolyzes a number of proteins, notably proteins on the surface of Gram-positive bacteria. It is therefore used for sample preparation in nucleic acid tests. However, ACP inhibits DNA amplification which makes its integration difficult. Heat is commonly used to inactivate ACP, but it can be challenging to integrate heating into point-of-care devices. Here, we use recombinase polymerase amplification (RPA) together with ACP, and show that when ACP is immobilized on nitrocellulose paper, it retains its enzymatic function and can easily and rapidly be activated using agitation. The nitrocellulose-bound ACP does, however, not leak into the solution, preventing the need for deactivation through heat or by other means. Nitrocellulose-bound ACP thus opens new possibilities for paper-based Point-of-Care (POC) devices.

Green Conducting Cellulose Yarns for Machine-Sewn Electronic Textiles.

The emergence of "green" electronics is a response to the pressing global situation where conventional electronics contribute to resource depletion and a global build-up of waste. For wearable applications, green electronic textile (e-textile) materials present an opportunity to unobtrusively incorporate sensing, energy harvesting, and other functionality into the clothes we wear. Here, we demonstrate electrically conducting wood-based yarns produced by a roll-to-roll coating process with an ink based on the biocompatible polymer:polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). The developed e-textile yarns display a, for cellulose yarns, record-high bulk conductivity of 36 Scm-1, which could be further increased to 181 Scm-1 by adding silver nanowires. The PEDOT:PSS-coated yarn could be machine washed at least five times without loss in conductivity. We demonstrate the electrochemical functionality of the yarn through incorporation into organic electrochemical transistors (OECTs). Moreover, by using a household sewing machine, we have manufactured an out-of-plane thermoelectric textile device, which can produce 0.2 µW at a temperature gradient of 37 K.

Multifunctional Nanocomposites with High Strength and Capacitance Using 2D MXene and 1D Nanocellulose.

The family of two-dimensional (2D) metal carbides and nitrides, known as MXenes, are among the most promising electrode materials for supercapacitors thanks to their high metal-like electrical conductivity and surface-functional-group-enabled pseudocapacitance. A major drawback of these materials is, however, the low mechanical strength, which prevents their applications in lightweight, flexible electronics. A strategy of assembling freestanding and mechanically robust MXene (Ti3 C2 Tx ) nanocomposites with one-dimensional (1D) cellulose nanofibrils (CNFs) from their stable colloidal dispersions is reported. The high aspect ratio of CNF (width of ≈3.5 nm and length reaching tens of micrometers) and their special interactions with MXene enable nanocomposites with high mechanical strength without sacrificing electrochemical performance. CNF loading up to 20%, for example, shows a remarkably high mechanical strength of 341 MPa (an order of magnitude higher than pristine MXene films of 29 MPa) while still maintaining a high capacitance of 298 F g-1 and a high conductivity of 295 S cm-1 . It is also demonstrated that MXene/CNF hybrid dispersions can be used as inks to print flexible micro-supercapacitors with precise dimensions. This work paves the way for fabrication of robust multifunctional MXene nanocomposites for printed and lightweight structural devices.

Layer-by-layer self-assembly of pillared two-dimensional multilayers.

We report Layer-by-Layer (LbL) self-assembly of pillared two-dimensional (2D) multilayers, from water, onto a wide range of substrates. This LbL method uses a small molecule, tris(2-aminoethyl) amine (TAEA), and a colloidal dispersion of Ti3C2Tx MXene to LbL self-assemble (MXene/TAEA)n multilayers, where n denotes the number of bilayers. Assembly with TAEA results in highly ordered (MXene/TAEA)n multilayers where the TAEA expands the interlayer spacing of MXene flakes by only ~ 1 Å and reinforces the interconnection between them. The TAEA-pillared MXene multilayers show the highest electronic conductivity of 7.3 × 104 S m-1 compared with all reported MXene multilayers fabricated by LbL technique. The (MXene/TAEA)n multilayers could be used as electrodes for flexible all-solid-state supercapacitors delivering a high volumetric capacitance of 583 F cm-3 and high energy and power densities of 3.0 Wh L-1 and 4400 W L-1, respectively. This strategy enables large-scale fabrication of highly conductive pillared MXene multilayers, and potentially fabrication of other 2D heterostructures.

From Single Molecules to Thin Film Electronics, Nanofibers, e-Textiles and Power Cables: Bridging Length Scales with Organic Semiconductors.

Organic semiconductors are the centerpiece of several vibrant research fields from single-molecule to organic electronics, and they are finding increasing use in bioelectronics and even classical polymer technology. The versatile chemistry and broad range of electronic functionalities of conjugated materials enable the bridging of length scales 15 orders of magnitude apart, ranging from a single nanometer (10-9 m) to the size of continents (106 m). This work provides a taste of the diverse applications that can be realized with organic semiconductors. The reader will embark on a journey from single molecular junctions to thin film organic electronics, supramolecular assemblies, biomaterials such as amyloid fibrils and nanofibrillated cellulose, conducting fibers and yarns for e-textiles, and finally to power cables that shuffle power across thousands of kilometers.

Electrical Textile Valves for Paper Microfluidics.

This paper describes electrically-activated fluidic valves that operate based on electrowetting through textiles. The valves are fabricated from electrically conductive, insulated, hydrophobic textiles, but the concept can be extended to other porous materials. When the valve is closed, the liquid cannot pass through the hydrophobic textile. Upon application of a potential (in the range of 100-1000 V) between the textile and the liquid, the valve opens and the liquid penetrates the textile. These valves actuate in less than 1 s, require low energy (≈27 µJ per actuation), and work with a variety of aqueous solutions, including those with low surface tension and those containing bioanalytes. They are bistable in function, and are, in a sense, the electrofluidic analog of thyristors. They can be integrated into paper microfluidic devices to make circuits that are capable of controlling liquid, including autonomous fluidic timers and fluidic logic.

Understanding the Dispersive Action of Nanocellulose for Carbon Nanomaterials.

This work aims at understanding the excellent ability of nanocelluloses to disperse carbon nanomaterials (CNs) in aqueous media to form long-term stable colloidal dispersions without the need for chemical functionalization of the CNs or the use of surfactant. These dispersions are useful for composites with high CN content when seeking water-based, efficient, and green pathways for their preparation. To establish a comprehensive understanding of such dispersion mechanism, colloidal characterization of the dispersions has been combined with surface adhesion measurements using colloidal probe atomic force microscopy (AFM) in aqueous media. AFM results based on model surfaces of graphene and nanocellulose further suggest that there is an association between the nanocellulose and the CN. This association is caused by fluctuations of the counterions on the surface of the nanocellulose inducing dipoles in the sp2 carbon lattice surface of the CNs. Furthermore, the charges on the nanocellulose will induce an electrostatic stabilization of the nanocellulose-CN complexes that prevents aggregation. On the basis of this understanding, nanocelluloses with high surface charge density were used to disperse and stabilize carbon nanotubes (CNTs) and reduced graphene oxide particles in water, so that further increases in the dispersion limit of CNTs could be obtained. The dispersion limit reached the value of 75 wt % CNTs and resulted in high electrical conductivity (515 S/cm) and high modulus (14 GPa) of the CNT composite nanopapers.

Coated and uncoated cellophane as materials for microplates and open-channel microfluidics devices.

This communication describes the use of uncoated cellophane (regenerated cellulose films) for the fabrication of microplates, and the use of coated cellophane for the fabrication of open-channel microfluidic devices. The microplates based on uncoated cellophane are particularly interesting for applications that require high transparency in the ultraviolet (UV) regime, and offer a low-cost alternative to expensive quartz-well plates. Uncoated cellophane is also resistant to damage by various solvents. The microfluidic devices, based on coated cellophane, can have features with dimensions as small as 500 µm, and complex, non-planar geometries. Electrodes can be printed on the surface of the coated cellophane, and embedded in microfluidic devices, to develop resistive heaters and electroanalytical devices for flow injection analysis, and continuous flow electrochemiluminescence (ECL) applications. These open-channel devices are appropriate for applications where optical transparency (especially in the visible regime), resistance to damage by water, biocompatibility and biodegradability are important. Cellophane microfluidic systems complement existing cellulose-based paper microfluidic systems, and provide an alternative to other materials used in microfluidics, such as synthetic polymers or glass. Cellulose films are plausible materials for uses in integrated microfluidic systems for diagnostics, analyses, cell-culture, and MEMS.

Fabrication of Nonperiodic Metasurfaces by Microlens Projection Lithography.

This paper describes a strategy that uses template-directed self-assembly of micrometer-scale microspheres to fabricate arrays of microlenses for projection photolithography of periodic, quasiperiodic, and aperiodic infrared metasurfaces. This method of "template-encoded microlens projection lithography" (TEMPL) enables rapid prototyping of planar, multiscale patterns of similarly shaped structures with critical dimensions down to ∼400 nm. Each of these structures is defined by local projection lithography with a single microsphere acting as a lens. This paper explores the use of TEMPL for the fabrication of a broad range of two-dimensional lattices with varying types of nonperiodic spatial distribution. The matching optical spectra of the fabricated and simulated metasurfaces confirm that TEMPL can produce structures that conform to expected optical behavior.

Integrating Electronics and Microfluidics on Paper.

Paper microfluidics and printed electronics have developed independently, and are incompatible in many aspects. Monolithic integration of microfluidics and electronics on paper is demonstrated. This integration makes it possible to print 2D and 3D fluidic, electrofluidic, and electrical components on paper, and to fabricate devices using them.

Electroanalytical devices with pins and thread.

This work describes the adaptive use of conventional stainless steel pins-used in unmodified form or coated with carbon paste-as working, counter, and quasi-reference electrodes in electrochemical devices fabricated using cotton thread or embossed omniphobic R(F) paper to contain the electrolyte and sample. For some applications, these pin electrodes may be easier to modify and use than printed electrodes, and their position and orientation can be changed as needed. Electroanalytical devices capable of multiplex analysis (thread-based arrays or 96-well plates) were easily fabricated using pins as electrodes in either thread or omniphobic R(F) paper.

Self-assembled three-dimensional and compressible interdigitated thin-film supercapacitors and batteries.

Traditional thin-film energy-storage devices consist of stacked layers of active films on two-dimensional substrates and do not exploit the third dimension. Fully three-dimensional thin-film devices would allow energy storage in bulk materials with arbitrary form factors and with mechanical properties unique to bulk materials such as compressibility. Here we show three-dimensional energy-storage devices based on layer-by-layer self-assembly of interdigitated thin films on the surface of an open-cell aerogel substrate. We demonstrate a reversibly compressible three-dimensional supercapacitor with carbon nanotube electrodes and a three-dimensional hybrid battery with a copper hexacyanoferrate ion intercalating cathode and a carbon nanotube anode. The three-dimensional supercapacitor shows stable operation over 400 cycles with a capacitance of 25 F g(-1) and is fully functional even at compressions up to 75%. Our results demonstrate that layer-by-layer self-assembly inside aerogels is a rapid, precise and scalable route for building high-surface-area 3D thin-film devices.

Paper-based potentiometric ion sensing.

This paper describes the design and fabrication of ion-sensing electrochemical paper-based analytical devices (EPADs) in which a miniaturized paper reference electrode is integrated with a small ion-selective paper electrode (ISPE) for potentiometric measurements. Ion-sensing EPADs use printed wax barriers to define electrochemical sample and reference zones. Single-layer EPADs for sensing of chloride ions include wax-defined sample and reference zones that each incorporate a Ag/AgCl electrode. In EPADs developed for other electrolytes (potassium, sodium, and calcium ions), a PVC-based ion-selective membrane is added to separate the sample zone from a paper indicator electrode. After the addition of a small volume (less than 10 µL) of sample and reference solutions to different zones, ion-sensing EPADs exhibit a linear response, over 3 orders of magnitude, in ranges of electrolyte concentrations that are relevant to a variety of applications, with a slope close to the theoretical value (59.2/z mV). Ion-selective EPADs provide a portable, inexpensive, and disposable way of measuring concentrations of electrolyte ions in aqueous solutions.

Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes.

It is challenging to obtain high-quality dispersions of single-wall nanotubes (SWNTs) in composite matrix materials, in order to reach the full potential of mechanical and electronic properties. The most widely used matrix materials are polymers, and the route to achieving high quality dispersions of SWNT is mainly chemical functionalization of the SWNT. This leads to increased cost, a loss of strength and lower conductivity. In addition full potential of colloidal self-assembly cannot be fully exploited in a polymer matrix. This may limit the possibilities for assembly of highly ordered structural nanocomposites. Here we show that nanofibrillated cellulose (NFC) can act as an excellent aqueous dispersion agent for as-prepared SWNTs, making possible low-cost exfoliation and purification of SWNTs with dispersion limits exceeding 40 wt %. The NFC:SWNT dispersion may also offer a cheap and sustainable alternative for molecular self-assembly of advanced composites. We demonstrate semitransparent conductive films, aerogels and anisotropic microscale fibers with nanoscale composite structure. The NFC:SWNT nanopaper shows increased strength at 3 wt % SWNT, reaching a modulus of 13.3 GPa, and a strength of 307 MPa. The anisotropic microfiber composites have maximum conductivities above 200 S cm(-1) and current densities reaching 1400 A cm(-2).