Integrated molybdenum single atom array sensors with multichannels for nitrite detection in foods.

Nitrite (NO2-) is present in a variety of foods, but the excessive intake of NO2- can indirectly lead to carcinogenic, teratogenic, mutagenicity and other risks to the human body. Therefore, the detection of NO2- is crucial for maintaining human health. In this study, an integrated array sensor for NO2- detection is developed based on molybdenum single atom material (IMSMo-SAC) using high-resolution electrohydrodynamic (EHD) printing technology. The sensor comprises three components: a printed electrode array, multichannels designed on polydimethylsiloxane (PDMS) and an electronic signal process device with bluetooth. By utilizing Mo-SAC to facilitate electron transfer during the redox reaction, rapid and efficient detection of NO2- can be achieved. The sensor has a wide linear range of 0.1 µM-107.8 mM, a low detection limit of 33 nM and a high sensitivity of 0.637 mA-1mM-1 cm-2. Furthermore, employing this portable array sensor allows simultaneously measurements of NO2- concentrations in six different foods samples with acceptable recovery rates. This array sensor holds great potential for detecting of small molecules in various fields.

Machine Learning-Assistant Colorimetric Sensor Arrays for Intelligent and Rapid Diagnosis of Urinary Tract Infection.

Urinary tract infections (UTIs), which can lead to pyelonephritis, urosepsis, and even death, are among the most prevalent infectious diseases worldwide, with a notable increase in treatment costs due to the emergence of drug-resistant pathogens. Current diagnostic strategies for UTIs, such as urine culture and flow cytometry, require time-consuming protocols and expensive equipment. We present here a machine learning-assisted colorimetric sensor array based on recognition of ligand-functionalized Fe single-atom nanozymes (SANs) for the identification of microorganisms at the order, genus, and species levels. Colorimetric sensor arrays are built from the SAN Fe1-NC functionalized with four types of recognition ligands, generating unique microbial identification fingerprints. By integrating the colorimetric sensor arrays with a trained computational classification model, the platform can identify more than 10 microorganisms in UTI urine samples within 1 h. Diagnostic accuracy of up to 97% was achieved in 60 UTI clinical samples, holding great potential for translation into clinical practice applications.

Nickel Single-Atom Catalyst Boosts Electrochemiluminescence of Graphitic Carbon Nitride for Sensitive Detection of HBV DNA.

Owing to excellent catalytic activity, single-atom catalysts (SACs) have recently attracted considerable research interest in the electrochemiluminescence (ECL) field. However, the applications of SACs are mostly limited to conventional luminol ECL system. Hence, it is necessary to explore the application of SACs in more ECL systems. In this work, nickel single-atom catalysts (Ni SACs) were successfully applied in the graphitic carbon nitride (g-C3N4)-H2O2 ECL system to significantly enhance its cathodic emission. Notably, g-C3N4 acted not only as an ECL luminophore but also as a support to anchor Ni SACs. Ni SACs can significantly activate H2O2 to produce abundant OH• radicals for enhancing the cathodic ECL emission of g-C3N4. Ni SACs-anchored g-C3N4 (Ni SACs@g-C3N4) had a 10-fold enhanced ECL intensity as compared to g-C3N4. Finally, the Ni SACs@g-C3N4-H2O2 ECL system was developed to detect hepatitis B virus (HBV) DNA by incorporating an entropy-driven DNA walking machine-assisted CRISPR-Cas12a amplification strategy. The constructed biosensor exhibited excellent detection performance for HBV DNA with a limit of detection as low as 17 aM. This work puts forward a new idea for enhancing the cathodic ECL of g-C3N4-H2O2 and expands the application of SACs in the ECL system.

A single-atom cobalt integrated flexible sensor for simultaneous detection of dihydroxybenzene isomers.

Simultaneous detection of dihydroxybenzene isomers including hydroquinone (HQ), catechol (CC), and resorcinol (RS) is significant for water quality control as they are highly toxic and often coexist. However, it is a great challenge to realize their accurate and simultaneous detection due to their similarity in structure and properties. Herein, an electrochemical flexible strip with single-atom cobalt (SA-Co/NG) was constructed through high-resolution electrohydrodynamic (EHD) printing for dihydroxybenzene isomer's simultaneous detection. Results showed that the provided SA-Co/NG strip exhibited excellent sensing performance with reliable repeatability, reproducibility, long-term stability, and flexibility. Linear ranges of 0.50-31 745 µM, 0.50-5909 µM, and 0.50-153.5 µM were achieved for HQ, CC, and RS, respectively, with a detection limit of 0.164 µM. Based on the experimental data, the mechanism concerning SA-Co/NG catalytic activity towards HQ can be deduced, starting from the combination of Co* and OH- in water, followed by the formation of Co-OH-dihydroxybenzene, and finally leading to O-H bond dissociation to generate benzoquinone. As for CC or RS, pyridinic N or CO synergistic with a single Co atom catalyzes their oxidation. Besides, the printed flexible SA-Co/NG strip further demonstrates the accurate and simultaneous detection of HQ, CC, and RS in textile wastewater, proposing a powerful practical application.

Integrated Biochip-Electronic System with Single-Atom Nanozyme for in Vivo Analysis of Nitric Oxide.

Nitric oxide (NO) exhibits a crucial role in various versatile and distinct physiological functions. Hence, its real-time sensing is highly important. Herein, we developed an integrated nanoelectronic system comprising a cobalt single-atom nanozyme (Co-SAE) chip array sensor and an electronic signal processing module (INDCo-SAE) for both in vitro and in vivo multichannel qualifying of NO in normal and tumor-bearing mice. The high atomic utilization and catalytic activity of Co-SAE endowed an ultrawide linear range for NO varying from 36 to 4.1 × 105 nM with a low detection limit of 12 nM. Combining in situ attenuated total reflectance surface enhanced infrared spectroscopy (ATR-SEIRAS) measurements and density function calculation revealed the activating mechanism of Co-SAE toward NO. The NO adsorption on an active Co atom forms *NO, followed by the reaction between *NO and OH-, which could help design relevant nanozymes. Further, we investigated the NO-producing behaviors of various organs of both normal and tumor-bearing mice using the proposed device. We also evaluated the NO yield produced by the wounded mouse using the designed device and found it to be approximately 15 times that of the normal mouse. This study bridges the technical gap between a biosensor and an integrated system for molecular analysis in vitro and in vivo. The as-fabricated integrated wireless nanoelectronic system with multiple test channels significantly improved the detection efficiency, which can be widely used in designing other portable sensing devices with multiplexed analysis capability.

Unique BiFeO3/g-C3N4 mushroom heterojunction with photocatalytic antibacterial and wound therapeutic activity.

Bacterial infections have become a major problem threatening public health, and it is of great significance to treat wound infections in biological systems caused by bacteria. However, traditionally used bacteriostatic agents usually cause additional pollution. Herein a mushroom-shaped clean and Green BiFeO3/g-C3N4 composite is employed for the first time for photocatalytic antibacterial activity and for the further promotion of wound healing. The ratio between BiFeO3 and g-C3N4 was delicately regulated to control the generated amount of ˙OH and ˙O2- by catalyzing the decomposition of hydrogen peroxide (H2O2) under illumination. Results show that 10%BFO/CN demonstrates the best performance for ˙OH and ˙O2- production, resulting in the highest antibacterial ability against E. coli and S. aureus. In addition, the catalytic mechanism of BiFeO3/g-C3N4 towards antibacterial activity is disclosed by a combination of ESR monitoring and analysis of the Mott-Schottky diagram. Furthermore, in vivo experiments prove that 10%BFO/CN can effectively promote anti-infection and wound healing in nude mice. This work sheds deep scientific insight on the synergistic effect of photocatalysis and photo-Fenton degradation as well as their application in antibacterial and wound therapeutic activity.

Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction.

The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.

Single-Atom Ruthenium Biomimetic Enzyme for Simultaneous Electrochemical Detection of Dopamine and Uric Acid.

Single-atom catalysts have attracted numerous attention due to the high utilization of metallic atoms, abundant active sites, and highly catalytic activities. Herein, a single-atom ruthenium biomimetic enzyme (Ru-Ala-C3N4) is prepared by dispersing Ru atoms on a carbon nitride support for the simultaneous electrochemical detection of dopamine (DA) and uric acid (UA), which are coexisting important biological molecules involving in many physiological and pathological aspects. The morphology and elemental states of the single-atom Ru catalyst are studied by transmission electron microscopy, energy dispersive X-ray elemental mapping, high-angle annular dark field-scanning transmission electron microscopy, and high-resolution X-ray photoelectron spectroscopy. Results show that Ru atoms atomically disperse throughout the C3N4 support by Ru-N chemical bonds. The electrochemical characterizations indicate that the Ru-Ala-C3N4 biosensor can simultaneously detect the oxidation of DA and UA with a separation of peak potential of 180 mV with high sensitivity and excellent selectivity. The calibration curves for DA and UA range from 0.06 to 490 and 0.5 to 2135 µM with detection limits of 20 and 170 nM, respectively. Moreover, the biosensor was applied to detect DA and UA in real biological serum samples using the standard addition method with satisfactory results.

Single-Atom Cobalt-Based Electrochemical Biomimetic Uric Acid Sensor with Wide Linear Range and Ultralow Detection Limit.

Uric acid (UA) detection is essential in diagnosis of arthritis, preeclampsia, renal disorder, and cardiovascular diseases, but it is very challenging to realize the required wide detection range and low detection limit. We present here a single-atom catalyst consisting of Co(II) atoms coordinated by an average of 3.4 N atoms on an N-doped graphene matrix (A-Co-NG) to build an electrochemical biomimetic sensor for UA detection. The A-Co-NG sensor achieves a wide detection range over 0.4-41,950 µM and an extremely low detection limit of 33.3 ± 0.024 nM, which are much better than previously reported sensors based on various nanostructured materials. Besides, the A-Co-NG sensor also demonstrates its accurate serum diagnosis for UA for its practical application. Combination of experimental and theoretical calculation discovers that the catalytic process of the A-Co-NG toward UA starts from the oxidation of Co species to form a Co3+-OH-UA*, followed by the generation of Co3+-OH + *UA_H, eventually leading to N-H bond dissociation for the formation of oxidized UA molecule and reduction of oxidized Co3+ to Co2+ for the regenerated A-Co-NG. This work provides a promising material to realize UA detection with wide detection range and low detection limit to meet the practical diagnosis requirements, and the proposed sensing mechanism sheds light on fundamental insights for guiding exploration of other biosensing processes.

Enhanced electrochemiluminescence from reduced graphene oxide-CdTe quantum dots for highly selective determination of copper ion.

An electrochemiluminescence (ECL) sensor based on reduced graphene oxide-CdTe quantum dots (RGO-CdTe QDs) composites for detecting copper ion (Cu2+ ) was proposed. The ECL behaviours of the RGO-CdTe QD modified electrode were investigated with H2 O2 as the co-reactant. Quantitative detection of Cu2+ was realized as Cu2+ could effectively quench the ECL signal of the RGO-CdTe QDs. A wide linear range of 1.00 × 10-14 to 1.00 × 10-4  M (R = 0.9953) was obtained under optimized conditions, and a detection limit (S/N = 3) was achieved of as low as 3.33 × 10-15  M. The proposed sensor also exhibited good stability and selectivity for the detection of copper ions. Finally, the analytical application of the proposed sensor was also evaluated using river water.

Shape-controlled ceria-reduced graphene oxide nanocomposites toward high-sensitive in situ detection of nitric oxide.

Nitric oxide (NO) is an important signal molecule released by most cancer cells under drug stimulation or/and disease development but it is extremely challenging to in situ while real-time sensitively detect NO due to its large diffusivity, low concentration and fast decay. Herein, shape-controlled reduced graphene oxide nanocomposing with ceria (rGO-CeO2) was synthesized via hydrothermal reaction to construct a highly sensitive real-time sensing platform for NO detection. The crystal shape of CeO2 nanoparticles in rGO-CeO2 composites significantly affects the sensing performance of rGO-CeO2, of which the regular hexagonal nanocrystal CeO2 achieves the highest sensitivity (1676.06 mA cm(-2) M(-1)), a wide dynamic range (18.0 nM to 5.6 µM) and a low detection limit (9.6 nM). This attributes to a synergical effect from high catalytic activity of the specifically shaped CeO2 nanocrystal and good conductivity/high surface area of rGO. This work demonstrates a way by rationally compose individual merit components while well control the nanostructure for a superior synergistic effect to build a smart sensing platform, while offering a great application potential to sensitively real-time detect NO released from living cells for diagnosis or/and studies of complicated biological processes.

Involvement of superoxide and nitric oxide in BRAF(V600E) inhibitor PLX4032-induced growth inhibition of melanoma cells.

The BRAF(V600E) inhibitor PLX4032 (Vemurafenib) is an FDA-approved new drug for the treatment of metastatic melanomas, which specifically inhibits the RAS/MEK/ERK signaling pathway to control cell proliferation and adhesion. However, no study has been carried out to investigate the role of intracellular oxidative balance in PLX4032-induced tumor growth inhibition. Herein, for the first time, superoxide (O2˙(-)) and nitric oxide (NO) generated from PLX4032-challenged melanoma cells were monitored using electrochemical sensors and conventional fluorescein staining techniques. Impacts of superoxide dismutase (SOD) and NG-monomethyl-L-arginine monoacetate (L-NMMA), a nitric oxide synthase inhibitor, were also examined to demonstrate the specificity of ROS/NO generation and its biological consequences. PLX4032 specifically triggers production of O2˙(-) and NO from BRAF(V600E) mutant A375 cells. SOD and L-NMMA could abolish the PLX4032-induced increase in intracellular O2˙(-) and NO production, thereby rescuing cell growth in BRAF mutant A375 cells (A375(BRAFV600E)). In addition, PLX4032 treatment could decrease the mitochondrial membrane potential in A375(BRAFV600E) cells. The results suggest that PLX4032 can selectively cause ROS production and depolarization of mitochondrial membranes, potentially initiating apoptosis and growth inhibition of PLX4032-sensitive cells. This work not only proposes a new mechanism for PLX4032-induced melanoma cell inhibition, but also highlights potential applications of electrochemical biosensors in cell biology and drug screening.

The construction of glucose biosensor based on platinum nanoclusters-multiwalled carbon nanotubes nanocomposites.

One-step synthesis method was proposed to obtain the nanocomposites of platinum nanoclusters and multiwalled carbon nanotubes (PtNCs-MWNTs), which were used as a novel immobilization matrix for the enzyme to fabricate glucose biosensor. The fabrication process of the biosensor was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscope. Due to the favorable characteristic of PtNCs-MWNTs nanocomposites, the biosensor exhibited good characteristics, such as wide linear range (3.0 µM-12.1 mM), low detection limit (1.0 µM), high sensitivity (12.8 µA mM⁻¹), rapid response time (within 6 s). The apparent Michaelis-Menten constant (K(app)(m)) is 2.1 mM. The performance of the resulting biosensor is more prominent than that of most of the reported glucose biosensors. Furthermore, it was demonstrated that this biosensor can be used for the assay of glucose in human serum samples.