Electrochemically Mediated Surface-Initiated de Novo Growth of Polymers for Amplified Electrochemical Detection of DNA.

The development of convenient and efficient strategies without involving any complex nanomaterials or enzymes for signal amplification is of great importance in bioanalytical applications. In this work, we report the use of electrochemically mediated surface-initiated atom transfer radical polymerization (SI-eATRP) as a novel amplification strategy based on the de novo growth of polymers (dnGOPs) for the electrochemical detection of DNA. Specifically, the capture of target DNA (tDNA) by the immobilized peptide nucleic acid (PNA) probes provides a high density of phosphate groups for the subsequent attachment of ATRP initiators onto the electrode surface by means of the phosphate-Zr4+-carboxylate chemistry, followed by the de novo growth of electroactive polymer via the SI-eATRP. De novo growth of long polymeric chains enables the labeling of numerous electroactive probes, which in turn greatly improves the electrochemical response. Moreover, it circumvents the slow kinetics and poor coupling efficiency encountered when nanomaterials or preformed polymers are used and features sufficient flexibility and simplicity in controlling the degree of signal amplification. Under optimal conditions, it allows a highly sensitive and selective detection of tDNA within a broad linear range from 0.1 fM to 0.1 nM (R2 = 0.996), with the detection limit down to 0.072 fM. Compared with the unamplified method, more than 1.2 × 106-fold sensitivity improvement in DNA detection can be achieved. By virtue of its simplicity, high efficiency, and cost-effectiveness, the proposed dnGOPs-based signal amplification strategy holds great potential in bioanalytical applications for the sensitive detection of biological molecules.

Interaction and charge transfer between isolated thylakoids and multi-walled carbon nanotubes.

Charge separation in photosynthetic light reactions has gained much interest in an attempt to fabricate biological photovoltaic devices through integration of photosynthetic material and conducting electrodes. Direct interaction between thylakoids, as representatives of photosynthetic materials, and multi-walled carbon nanotubes (MWCNTs) is expected to increase charge transfer. Thylakoids are isolated from spinach leaf chloroplasts and pristine MWCNTs are dispersed in Triton X-100 (TX-100) as a surfactant to retain their electronic properties through non-covalent interactions. The Raman and UV-Vis spectra suggest close interactions between the thylakoids and the MWCNTs. Stable thylakoids including the embedded protein subunits and light harvesting antennas can be detected from the non-shifted 680 nm absorbance peak. The 50% fluorescence quenching in the MWCNTs-thylakoids preparation as compared to thylakoids alone using single wavelength excitation suggests charge transfer between the thylakoids and the MWCNTs.

High-Throughput Manufacturing of Multimodal Epidermal Mechanosensors with Superior Detectability Enabled by a Continuous Microcracking Strategy.

Non-invasive human-machine interactions (HMIs) are expected to be promoted by epidermal tactile receptive devices that can accurately perceive human activities. In reality, however, the HMI efficiency is limited by the unsatisfactory perception capability of mechanosensors and the complicated techniques for device fabrication and integration. Herein, a paradigm is presented for high-throughput fabrication of multimodal epidermal mechanosensors based on a sequential "femtosecond laser patterning-elastomer infiltration-physical transfer" process. The resilient mechanosensor features a unique hybrid sensing layer of rigid cellular graphitic flakes (CGF)-soft elastomer. The continuous microcracking of CGF under strain enables a sharp reduction in conductive pathways, while the soft elastomer within the framework sustains mechanical robustness of the structure. As a result, the mechanosensor achieves an ultrahigh sensitivity in a broad strain range (GF of 371.4 in the first linear range of 0-50%, and maximum GF of 8922.6 in the range of 61-70%), a low detection limit (0.01%), and a fast response/recovery behavior (2.6/2.1 ms). The device also exhibits excellent sensing performances to multimodal mechanical stimuli, enabling high-fidelity monitoring of full-range human motions. As proof-of-concept demonstrations, multi-pixel mechanosensor arrays are constructed and implemented in a robot hand controlling system and a security system, providing a platform toward efficient HMIs.

Gradiently Foaming Ultrasoft Hydrogel with Stop Holes for Highly Deformable, Crack-Resistant and Sensitive Conformal Human-Machine Interfaces.

Hydrogels are considered as promising materials for human-machine interfaces (HMIs) owing to their merits of tailorable mechanical and electrical properties; nevertheless, it remains challenging to simultaneously achieve ultrasoftness, good mechanical robustness and high sensitivity, which are the pre-requisite requirements for wearable sensing applications. Herein, for the first time, this work proposes a universal phase-transition-induced bubbling strategy to fabricate ultrasoft gradient foam-shaped hydrogels (FSHs) with stop holes for high deformability, crack-resistance and sensitive conformal HMIs. As a typical system, the FSH based on polyacrylamide/sodium alginate system shows an ultralow Young's modulus (1.68 kPa), increased sustainable strain (1411%), enhanced fracture toughness (915.6 J m-2), improved tensile sensitivity (21.77), and compressive sensitivity (65.23 kPa-1). The FSHs are used for precisely acquiring and identifying gesture commands of the operator to remotely control a surgical robot for endoscopy and an electric ship in a first-person perspective for cruising, feeding crabs and monitoring the environmental change in real-time.

Tough Adhesive, Antifreezing, and Antidrying Natural Globulin-Based Organohydrogels for Strain Sensors.

Hydrogels are often used to fabricate strain sensors; however, they also suffer from freezing at low temperatures and become dry during long-time storage. Encapsulation of hydrogels with elastomers is one of the methods to solve these problems although the adhesion between hydrogels and elastomers is usually low. In this work, using bovine serum protein (BSA) as the natural globulin model and glycerol/H2O as the mixture solvent, BSA/polyacrylamide organohydrogels (BSA/PAAm OHGs) were prepared by a facile photopolymerization approach. At the optimal condition, BSA/PAAm OHG demonstrated not only high toughness but also tough adhesion properties, which could strongly adhere to various substrates, such as glass, metals, rigid polymeric materials (even poly(tetrafluoroethylene), i.e., PTFE), and soft elastomers. Moreover, BSA/PAAm OHG was flexible and showed tough adhesion at -20 °C. The toughening mechanism and the adhesive mechanism were proposed. On being encapsulated by poly(dimethylsiloxane) (PDMS), it illustrated good antidrying performance. After introducing a conductive filler, the encapsulated BSA/PAAm OHG could be used as a strain sensor to detect human motions. This work provides a better understanding of the adhesive mechanism of natural protein-based organohydrogels.

Solution-Processed Sensing Textiles with Adjustable Sensitivity and Linear Detection Range Enabled by Twisting Structure.

Wearable strain sensors are emerging rapidly for their promising applications in human motion detection for diagnosis, healthcare, training instruction, and rehabilitation exercise assessment. However, it remains a bottleneck in gaining comfortable and breathable devices with the features of high sensitivity, linear response, and tunable detection range. Textiles possess fascinating advantages of good breathability, aesthetic property, tailorability, and excellent mechanical compliance to conformably attach to human body. As the meandering loops in a textile can be extended in different directions, it provides plenty of room for exploring ideal sensors by tuning a twisting structure with rationally selected yarn materials. Herein, textile sensors with twisting architecture are designed via a solution-based process by using a stable water-based conductive ink that is composed of polypyrrole/polyvinyl alcohol nanoparticles with a mean diameter of 50 nm. Depending on the predesigned twisting models, the thus-fabricated textile sensors show adjustable performances, exhibiting a high sensitivity of 38.9 with good linearity and a broad detection range of 200%. Such sensors can be integrated into fabrics and conformably attached to skin for monitoring subtle (facial expressions, breathing, and speaking) and large (stretching, jumping, running and jogging, and sign language) human motions. As a proof-of-concept application, by integrating with a wireless transmitter, the signals detected by our sensors during exercise (e.g., running) can be remotely received and displayed on a smartphone. It is believed that the integration of our textile sensors with selected twisting models into a cloth promises full-range motion detection for wearable electronics and human-machine interfaces.

Conductive regenerated silk-fibroin-based hydrogels with integrated high mechanical performances.

Regenerated silk fibroin hydrogels (RSF gels) are extensively investigated in the biomedical field. However, the mechanical properties of RSF hydrogels are often weak or brittle, which limits their potential for applications where high strength is required. Herein, strong and tough RSF-based hydrogels with large extensibility and rapid self-recovery property were developed via the double network (DN) concept. RSF/HPAAm DN gels, consisting of a physical RSF/SDS gel as the first network and a physically cross-linked HPAAm as the second network, are fully physical network structures. At optimal conditions, the RSF/HPAAm DN gel exhibited integrated high mechanical properties, including high compressive strength (122 MPa), high tensile strength (σf of 1.17 MPa), large extensibility (εf of 19.03 mm mm-1), high toughness (W of 11.75 MJ m-3 and T of 1769 J m-2) and rapid self-recovery (61% toughness recovery after 1 min of resting at room temperature). Interestingly, owing to contained sodium dodecyl sulfate (SDS) and NaCl, RSF/HPAAm DN gels also displayed ionic conductivity, which could be used as a strain sensor, a touch screen pen and the electronic skin of artificial robots. We believe that this design strategy as well as our RSF/HPAAm DN gel will provide a new route for achieving high performance RSF-based gels with new functionalities.

Ultrasensitive Anti-Interference Voice Recognition by Bio-Inspired Skin-Attachable Self-Cleaning Acoustic Sensors.

Human voice recognition systems (VRSs) are a prerequisite for voice-controlled human-machine interfaces (HMIs). In order to avoid interference from unexpected background noises, skin-attachable VRSs are proposed to directly detect physiological mechanoacoustic signals based on the vibrations of vocal cords. However, the sensitivity and response time of existing VRSs are bottlenecks for efficient HMIs. In addition, water-based contaminants in our daily lives, such as skin moisture and raindrops, normally result in performance degradation or even functional failure of VRSs. Herein, we present a skin-attachable self-cleaning ultrasensitive and ultrafast acoustic sensor based on a reduced graphene oxide/polydimethylsiloxane composite film with bioinspired microcracks and hierarchical surface textures. Benefitting from the synergetic effect of the spider-slit-organ-like multiscale jagged microcracks and the lotus-leaf-like hierarchical structures, our superhydrophobic VRS exhibits an ultrahigh sensitivity (gauge factor, GF = 8699), an ultralow detection limit (ε = 0.000 064%), an ultrafast response/recovery behavior, an excellent device durability (>10 000 cycles), and reliable detection of acoustic vibrations over the audible frequency range (20-20 000 Hz) with high signal-to-noise ratios. These superb performances endow our skin-attachable VRS with anti-interference perception of human voices with high precision even in noisy environments, which will expedite the voice-controlled HMIs.