Fully Integrated Multiplexed Wristwatch for Real-Time Monitoring of Electrolyte Ions in Sweat.

Considerable progress has already been made in sweat sensors based on electrochemical methods to realize real-time monitoring of biomarkers. However, realizing long-term monitoring of multiple targets at the atomic level remains extremely challenging, in terms of designing stable solid contact (SC) interfaces and fully integrating multiple modules for large-scale applications of sweat sensors. Herein, a fully integrated wristwatch was designed using mass-manufactured sensor arrays based on hierarchical multilayer-pore cross-linked N-doped porous carbon coated by reduced graphene oxide (NPCs@rGO-950) microspheres with high hydrophobicity as core SC, and highly selective monitoring simultaneously for K+, Na+, and Ca2+ ions in human sweat was achieved, exhibiting near-Nernst responses almost without forming an interfacial water layer. Combined with computed tomography, solid-solid interface potential diffusion simulation results reveal extremely low interface diffusion potential and high interface capacitance (598 µF), ensuring the excellent potential stability, reversibility, repeatability, and selectivity of sensor arrays. The developed highly integrated-multiplexed wristwatch with multiple modules, including SC, sensor array, microfluidic chip, signal transduction, signal processing, and data visualization, achieved reliable real-time monitoring for K+, Na+, and Ca2+ ion concentrations in sweat. Ingenious material design, scalable sensor fabrication, and electrical integration of multimodule wearables lay the foundation for developing reliable sweat-sensing systems for health monitoring.

Highly Stable Solid Contact Calcium Ion-Selective Electrodes: Rapid Ion-Electron Transduction Triggered by Lipophilic Anions Participating in Redox Reactions of CunS Nanoflowers.

Solid contact (SC) calcium ion-selective electrodes (Ca2+-ISEs) have been widely applied in the analysis of water quality and body fluids by virtue of the unique advantages of easy operation and rapid response. However, the potential drift during the long-term stability test hinders their further practical applications. Designing novel redox SC layers with large capacitance and high hydrophobicity is a promising approach to stabilize the potential stability, meanwhile, exploring the transduction mechanism is also of great guiding significance for the precise design of SC layer materials. Herein, flower-like copper sulfide (CunS-50) composed of nanosheets is meticulously designed as the redox SC layer by modification with the surfactant (CTAB). The CunS-50-based Ca2+-ISE (CunS-50/Ca2+-ISE) demonstrates a near-Nernstian slope of 28.23 mV/dec for Ca2+ in a wide activity linear range of 10-7 to 10-1 M, with a low detection limit of 3.16 × 10-8 M. CunS-50/Ca2+-ISE possesses an extremely low potential drift of only 1.23 ± 0.13 µV/h in the long-term potential stability test. Notably, X-ray absorption fine-structure (XAFS) spectra and electrochemical experiments are adopted to elucidate the transduction mechanism that the lipophilic anion (TFPB-) participates in the redox reaction of CunS-50 at the solid-solid interface of ion-selective membrane (ISM) and redox inorganic SC layer (CunS-50), thereby promoting the generation of free electrons to accelerate ion-electron transduction. This work provides an in-depth comprehension of the transduction mechanism of the potentiometric response and an effective strategy for designing redox materials of ion-electron transduction triggered by lipophilic anions.

Highly Accurate Determination of the Total Amount of Pb2+ and Pb(OH)+ in a Natural Water Environment Revealed by Dynamic Simulation and DFT Calculation: Benefit from the Electron Inverse Effect of Pt Nanoclusters over Defective g-C3N4.

Although utilizing nanomaterial-modified electrodes for lead ion detection has achieved great success, most of them are carried out under acidic conditions and ignore the variation of Pb(II) speciation at different pH conditions, leading to the potential inaccuracy of Pb(II) detection in a neutral natural water environment. Thus, designing a novel catalyst with high accuracy for the detection of various forms of the total amount of Pb(II) (Pb2+ and Pb(OH)+) in neutral waters is significant. Herein, Pt nanoclusters (Pt NCs) were elaborately constructed and stabilized on the Co single-atom-doped g-C3N4 with abundant N vacancies (Pt NCs/VN-C3N4), which achieved the ultrasensitive detection (102.16 µM µA-1) of Pb(II) in neutral conditions. The dynamic simulation and theoretical calculations reveal that the parallel deposition of Pb2+ and Pb(OH)+ occurs on the electrode surface modified by Pt NCs/VN-C3N4, and the current peaks of Pb(II) are cocontributed by Pb2+ and Pb(OH)+ species. An "electron inverse" phenomenon in Pt NCs/VN-C3N4 from the VN-C3N4 substrate to Pt NCs endows Pt NCs in an electron-rich state, serving as active centers to promote rapid and efficient reduction for both Pb2+ and Pb(OH)+, facilitating the accurate detection of the total amount of Pb(II) in all forms in the actual water environment.

Ion-Electron Transduction Layer of the SnS2-MoS2 Heterojunction to Elevate Superior Interface Stability for All-Solid Sodium-Ion Selective Electrode.

The high selectivity and fast ion response of all-solid sodium ion selective electrodes were widely applied in human sweat analysis. However, the potential drift due to insufficient interfacial capacitance leads to the deterioration of its stability and ultimately affects the potential accuracy of ion analysis. Designing a novel ion-electron transduction layer between the electrode and the ion selective membrane is an effective method to stabilize the interfacial potential. Herein, the SnS2-MoS2 heterojunction material was constructed by doping Sn in MoS2 nanosheets and used as the ion electron transduction layers of an all-solid sodium ion selective electrode for the first time, achieving the stable and efficient detection of Na+ ions. The proposed electrode exhibited a Nernst slope of 57.86 mV/dec for the detection of Na+ ions with a detection limit of 10-5.7 M in the activity range of 10-6-10-1 M. Via the electronic interaction at the heterojunction interfaces between SnS2 and MoS2 materials, the micro-nanostructure of the SnS2-MoS2 heterojunction was changed and SnS2-MoS2 as the ion-electron transduction layer acquired excellent capacitance (699 µF) and hydrophobicity (132°), resulting in a long-term potential stability of 1.37 µV/h. It was further proved that the large capacitance and high hydrophobicity of the ion-electron transduction layer are primary reasons for the excellent stability of the all-solid sodium ion selective electrode toward Na+ ions.

Interface catalytic regulation via electron rearrangement and hydroxyl radicals triggered by oxygen vacancies and heavy metal ions.

Although the enhanced intrinsic activities of some nano-metal oxides are obtained by manufacturing oxygen vacancies (OVs), the effect of multiple roles of OVs is ambiguous. Herein, an interface catalytic regulation via electron rearrangement and hydroxyl radicals (˙OH) was proposed with the designed ZrO2 hollow sphere rich in OVs (Vo-rich ZrO2). Surprisingly, it was shown that the catalytic ability of Vo-rich ZrO2 was 9.9 times higher than that of ZrO2 with little OVs in electrochemical catalytic reduction of Pb(ii). It was found that the generation of Zr2+ and Zr3+ caused by OVs results in the rearrangement of abundant free electrons to facilitate the catalytic reaction rates. The longer bond length between Vo-rich ZrO2 and reactants, and the lower adsorption energy are beneficial for reactants to desorb, improving the conversion rates. Besides, the produced ˙OH were captured which were induced by OVs and trace divalent heavy metal ions in in situ electron paramagnetic resonance (EPR) experiments, contributing to lowering the energy barriers. This study not only revealed the enhanced interface catalytic effect of electron rearrangement and generated ˙OH triggered by OVs, but also provided unique insights into interface catalytic regulation on nano-metal oxides simulated by OVs.

Generalizable Descriptors of Highly Sensitive Detection of As(III) over Transition-Metal Single Atoms: A Combined Density Function Theory and Gradient Boosting Regression Approach.

Traditional nanomodified electrodes have made great achievements in electrochemical stripping voltammetry of sensing materials for As(III) detection. Moreover, the intermediate states are complicated to probe because of the ultrashort lifetime and complex reaction conditions of the electron transfer process in electroanalysis, which seriously hinder the identification of the actual active site. Herein, the intrinsic interaction of highly sensitive analytical behavior of nanomaterials is elucidated from the perspective of electronic structure through density functional theory (DFT) and gradient boosting regression (GBR). It is revealed that the atomic radius, d-band center (εd), and the largest coordinative TM-N bond length play a crucial role in regulating the arsenic reduction reaction (ARR) performance by the established ARR process for 27 sets of transition-metal single atoms supported on N-doped graphene. Furthermore, the database composed of filtered intrinsic electronic structural properties and the calculated descriptors of the central metal atom in TM-N4-Gra were also successfully extended to oxygen evolution reaction (OER) systems, which effectively verified the reliability of the whole approach. Generally, a multistep workflow is developed through GBR models combined with DFT for valid screening of sensing materials, which will effectively upgrade the traditional trial-and-error mode for electrochemical interface designing.

General Strategies to Construct Highly Efficient Sensing Interfaces for Metal Ions Detection from the Perspective of Catalysis.

Constructing high-effective electrode sensing interfaces has been considered an effective method for electrochemical detection toward heavy metal ions (HMIs). However, most research has been devoted to enhancing the stripping currents of HMIs by simply improving the adsorptive capacity and conductivity of the electrode modified materials, while lacking theoretical guidelines in fabricating catalytic sensing interfaces. Besides, the understanding of detection mechanisms is quite unscientific from the perspective of catalysis. This perspective summarizes five general strategies in designing highly efficient sensing interfaces in the recent five years, including modulating crystal phases, orientations and planes, defect engineering, ionic valence state cycle engineering, adsorption in situ catalysis strategy, and construction of atomic level catalytic active sites. What's more, the catalytic mechanisms for improving the signals of HMIs, such as boosting the electron transfer rates and conversion rates, lowering the energy barriers, etc., are introduced and emphasized. This study has a great significance in directionally controlling functionalized electrochemical sensors to achieve excellent sensitivity and selectivity in detecting environmental pollutants from the view of catalysis, and it also brings enlightenments and guidance to develop new electroanalytical methods.

Growth inhibition effect of ß-catenin small interfering RNA-mediated gene silencing on human colon carcinoma HT-29 cells.

The ß-catenin gene is a critical component of Wnt signaling pathway. Aberrant activation of Wnt/ß-catenin signaling and subsequent upregulation of ß-catenin is related to enhancing cell proliferation and developing colon polyps and colon cancer. In the present study, the effect of ß-catenin knockdown on the growth and survival of the human colon cancer cell line HT-29 was investigated in vitro. The effect of knockdown of ß-catenin on cell proliferation was investigated by MTT assay and colony formation. The cell cycle distribution was investigated by flow cytometry. Apoptosis was measured by nuclear staining and flow cytometry. The change of ß-catenin and related proteins were determined by western blotting and immunofluorescence. The results showed that small interfering RNA directed against ß-catenin markedly inhibited the expression and nuclear translocation of ß-catenin and decreased the expression of known target genes such as cyclin D1 and c-myc; HT-29 cell proliferation was inhibited as indicated by growth reduction, cell cycle arrest in G0/G1 phase, and induction of apoptosis; and the inhibition of cell growth may be associated with switching off cyclin D1 and c-myc expression by small interfering RNA targeted against ß-catenin in colon cancer HT-29 cells.