Directly Using Ti3C2Tx MXene for a Solid-Contact Potentiometric pH Sensor toward Wearable Sweat pH Monitoring.

The level of hydrogen ions in sweat is one of the most important physiological indexes for the health state of the human body. As a type of two-dimensional (2D) material, MXene has the advantages of superior electrical conductivity, a large surface area, and rich functional groups on the surface. Herein, we report a type of Ti3C2Tx-based potentiometric pH sensor for wearable sweat pH analysis. The Ti3C2Tx was prepared by two etching methods, including a mild LiF/HCl mixture and HF solution, which was directly used as the pH-sensitive materials. Both etched Ti3C2Tx showed a typical lamellar structure and exhibited enhanced potentiometric pH responses compared with a pristine precursor of Ti3AlC2. The HF-Ti3C2Tx disclosed the sensitivities of -43.51 ± 0.53 mV pH-1 (pH 1-11) and -42.73 ± 0.61 mV pH-1 (pH 11-1). A series of electrochemical tests demonstrated that HF-Ti3C2Tx exhibited better analytical performances, including sensitivity, selectivity, and reversibility, owing to deep etching. The HF-Ti3C2Tx was thus further fabricated as a flexible potentiometric pH sensor by virtue of its 2D characteristic. Upon integrating with a solid-contact Ag/AgCl reference electrode, the flexible sensor realized real-time monitoring of pH level in human sweat. The result disclosed a relatively stable pH value of ~6.5 after perspiration, which was consistent with the ex situ sweat pH test. This work offers a type of MXene-based potentiometric pH sensor for wearable sweat pH monitoring.

A Solid-Contact Reference Electrode Based on Silver/Silver Organic Insoluble Salt for Potentiometric Ion Sensing.

Solid-contact ion-selective electrodes are a type of ion measurement devices that have been focused in wearable biotechnology based on the features of miniaturization and integration. However, the solid-contact reference electrodes (SC-REs) remain relatively less focused compared with numerous working (or indicator) electrodes. Most SC-REs in wearable sensors rely on Ag/AgCl reference electrodes with solid electrolytes, for example, the hydrophilic electrolyte salts in polymer matrix, but face the risk of electrolyte leakage. Herein, we report a type of SC-REs based on the silver/silver tetraphenylborate (Ag/AgTPB) organic insoluble electrode. The SC-RE consists of a Ag substrate, a solid contact (AgTPB), and a plasticized poly(vinyl chloride) (PVC) membrane containing the hydrophobic organic salt of tetrabutylammonium tetraphenylborate (TBATPB). The potentiometric measurements demonstrated that the SC-RE of Ag/AgTPB/PVC-TBATPB showed a reproducible standard potential in various electrolytes and disclosed high long-term stability. This SC-RE was further fabricated on a flexible substrate and integrated into all-solid-state wearable potentiometric ion sensor for sweat Cl- monitoring.

Carbon-Based Transducers for Solid-Contact Calcium Ion-Selective Electrodes: Mesopore and Nitrogen-Doping Effects.

Solid-contact ion-selective electrodes (SC-ISEs) exhibit great potential in the detection of routine and portable ions which rely on solid-contact (SC) materials for the transduction of ions to electron signals. Carbon-based materials are state-of-the-art SC transducers due to their high electrical double-layer (EDL) capacitance and hydrophobicity. However, researchers have long searched for ways to enhance the interfacial capacitance in order to improve the potential stability. Herein, three representative carbon-based SC materials including nitrogen-doped mesoporous carbon (NMC), reduced graphene oxide (RGO), and carbon nanotubes (CNT) were compared. The results disclose that the NMC has the highest EDL capacitance owing to its mesopore structure and N-doping while maintaining high hydrophobicity so that no obvious water-layer effect was observed. The Ca2+-SC-ISEs based on the SC of NMC exhibited high potential stability compared with RGO and CNT. This work offers a guideline for the development of carbon-material-based SC-ISEs through mesoporous and N-doping engineering to improve the interfacial capacitance. The developed NMC-based solid-contact Ca2+-SC-ISE exhibited a Nernstian slope of 26.3 ± 3.1 mV dec-1 ranging from 10 µM to 0.1 M with a detection limit of 3.2 µM. Finally, a practical application using NMC-based SC-ISEs was demonstrated through Ca2+ ion analysis in mineral water and soil leaching solutions.

Cryo-EM structure of isomeric molluscan hemocyanin triggered by viral infection.

Hemocyanins (Hcs) of arthropods and mollusks function not only as oxygen transporters, but also as phenoloxidases (POs). In invertebrates, PO is an important component in the innate immune cascade, where it functions as the initiator of melanin synthesis, a pigment involved in encapsulating and killing of pathogenic microbes. Although structures of Hc from several species of invertebrates have been reported, the structural basis for how PO activity is triggered by structural changes of Hc in vivo remains poorly understood. Here, we report a 6.8 Å cryo-electron microscopy (cryo-EM) structure of the isomeric form of hemocyanin, which was isolated from Abalone Shriveling syndrome-associated Virus (AbSV) infected abalone (Halitotis diversicolor), and build a pseudoatomic model of isomeric H. diversicolor hemocyanin 1 (HdH1). Our results show that, compared with native form of HdH1, the architecture of isomeric HdH1 turns into a more relaxed form. The interactions between certain functional units (FUs) present in the native form of Hc either decreased or were totally abolished in the isomeric form of Hc. As a result of that, native state Hc switches to its isomeric form, enabling it to play its role in innate immune responses against invading pathogens.