Nanoarchitectonics-based electrochemical aptasensors for highly efficient exosome detection.

Exosomes, a type of extracellular vesicles, have attracted considerable attention due to their ability to provide valuable insights into the pathophysiological microenvironment of the cells from which they originate. This characteristic implicates their potential use as diagnostic disease biomarkers clinically, including cancer, infectious diseases, neurodegenerative disorders, and cardiovascular diseases. Aptasensors, which are electrochemical aptamers based biosensing devices, have emerged as a new class of powerful detection technology to conventional methods like ELISA and Western analysis, primarily because of their capability for high-performance bioanalysis. This review covers the current research landscape on the detection of exosomes utilizing nanoarchitectonics strategy for the development of electrochemical aptasensors. Strategies involving signal amplification and biofouling prevention are discussed, with an emphasis on nanoarchitectonics-based bio-interfaces, showcasing their potential to enhance sensitivity and selectivity through optimal conduction and mass transport properties. The ongoing challenges to broaden the clinical applications of these biosensors are also highlighted.

This review emphasizes the significant impact of integrating nanoarchitectonics into aptamer-based electrochemical biosensors for exosome detection, thereby enhancing early disease detection and monitoring disease progression in clinical settings.

Enhancing Substrate Channeling with Multi-Enzyme Architectures in Hydrogen-Bonded Organic Framework.

Hydrogen-bonded organic frameworks (HOF) represent an emerging category of organic structures with high crystallinity and metal-free, which are not commonly observed in alternative porous organic frameworks. These needle-like porous structure can help in stabilizing enzymes and allow transfer of molecules between enzymes participating in cascade reactions for enhanced substrate channelling. Herein, we systematically synthesized and investigated the stability of HOF at extreme conditions followed by one-pot encapsulation of single and bi-enzyme systems. Firstly, we observed HOF to be stable at pH 1 to 14 and at high temperatures (up to 115°C). Secondly, the encapsulated glucose oxidase enzyme (GOX) showed 80 % and 90% of its original activity at 70 °C and pH 11, respectively. Thirdly, transient time close to 0 seconds was observed for HOF encapsulated bi-enzyme cascade reaction system demonstrating a 4.25-fold improvement in catalytic activity when compared to free enzymes with enhanced substrate channelling. Our findings showcase a facile system synthesized under ambient conditions to encapsulate and stabilize enzymes at extreme conditions.

Nanochemistry of gold: from surface engineering to dental healthcare applications.

Advancements in nanochemistry have led to the development of engineered gold nanostructures (GNSs) with remarkable potential for a variety of dental healthcare applications. These innovative nanomaterials offer unique properties and functionalities that can significantly improve dental diagnostics, treatment, and overall oral healthcare applications. This review provides an overview of the latest advancements in the design, synthesis, and application of GNSs for dental healthcare applications. Engineered GNSs have emerged as versatile tools, demonstrating immense potential across different aspects of dentistry, including enhanced imaging and diagnosis, prevention, bioactive coatings, and targeted treatment of oral diseases. Key highlights encompass the precise control over GNSs' size, crystal structure, shape, and surface functionalization, enabling their integration into sensing, imaging diagnostics, drug delivery systems, and regenerative therapies. GNSs, with their exceptional biocompatibility and antimicrobial properties, have demonstrated efficacy in combating dental caries, periodontitis, peri-implantitis, and oral mucosal diseases. Additionally, they show great promise in the development of advanced sensing techniques for early diagnosis, such as nanobiosensor technology, while their role in targeted drug delivery, photothermal therapy, and immunomodulatory approaches has opened new avenues for oral cancer therapy. Challenges including long-term toxicity, biosafety, immune recognition, and personalized treatment are under rigorous investigation. As research at the intersection of nanotechnology and dentistry continues to thrive, this review highlights the transformative potential of engineered GNSs in revolutionizing dental healthcare, offering accurate, personalized, and minimally invasive solutions to address the oral health challenges of the modern era.

Ultra-trace Ag doped carbon quantum dots with peroxidase-like activity for the colorimetric detection of glucose.

Carbon quantum dots (CQDs) have significant applications in nanozymes. However, previous studies have not elucidated the structure-activity relationship and enzyme mechanism. In this study, we employed a one-step microwave method to synthesize ultra-trace Ag-doped carbon quantum dots (Ag-CQDs). In the presence of hydrogen peroxide (H2O2), we used the oxidative coupling reaction of 3,3',5,5'-tetramethylbenzidine (TMB) to evaluate the intrinsic peroxidase-like activity, kinetics, and mechanism of Ag-CQDs. The trace amount of doped Ag (1.64 %) facilitated electron transfer from the CQDs interior to the surface. The electron transfer triggered the peroxide activity of CQDs, producing hydroxyl radical (·OH), which oxidized the colorless TMB to blue-colored TMB (oxTMB). By coupling with glucose oxidase (GOx), the Ag-CQDs/H2O2/TMB system has been used for colorimetric glucose determination. The system demonstrated a low detection limit (0.17 µM), wide linear range (0.5-5.5 µM), and satisfactory results when fruit juice was analyzed. This study reports a feasible method for the colorimetric detection of glucose by synthesizing ultra-trace Ag-doped carbon quantum dots with peroxidase-mimicking activity.

A self-powered electrochemical aptasensor for the detection of 17ß-estradiol based on carbon nanocages/gold nanoparticles and DNA bioconjugate mediated biofuel cells.

17ß-Estradiol (E2) is an important endogenous estrogen, which disturbs the endocrine system and poses a threat to human health because of its accumulation in the human body. Herein, a biofuel cell (BFC)-based self-powered electrochemical aptasensor was developed for E2 detection. Porous carbon nanocage/gold nanoparticle composite modified indium tin oxide (CNC/AuNP/ITO) and glucose oxidase modified CNC/AuNP/ITO were used as the biocathode and bioanode of BFCs, respectively. [Fe(CN)6]3- was selected as an electroactive probe, which was entrapped in the pores of positively charged magnetic Fe3O4 nanoparticles (PMNPs) and then capped with a negatively charged E2 aptamer to form a DNA bioconjugate. The presence of the target E2 triggered the entrapped [Fe(CN)6]3- probe release due to the removal of the aptamer via specific recognition, which resulted in the transfer of electrons produced by glucose oxidation at the bioanode to the biocathode and produced a high open-circuit voltage (EOCV). Consequently, a "signal-on" homogeneous self-powered aptasensor for E2 assay was realized. Promisingly, the BFC-based self-powered aptasensor has particularly high sensitivity for E2 detection in the concentration range of 0.5 pg mL-1 to 15 ng mL-1 with a detection limit of 0.16 pg mL-1 (S/N = 3). Therefore, the proposed BFC-based self-powered electrochemical aptasensor has great promise to be applied as a successful prototype of a portable and on-site bioassay in the field of environment monitoring and food safety.

Nel-like Molecule Type 1 Combined with Gold Nanoparticles Modulates Macrophage Polarization, Osteoclastogenesis, and Oral Microbiota in Periodontitis.

The disruption of host-microbe homeostasis and uncontrolled inflammatory response have been considered as vital causes for developing periodontitis, subsequently leading to an imbalance between the bone and immune system and the collapse of bone homeostasis. Consequently, strategies to modulate the immune response and bone metabolization have become a promising approach to prevent and treat periodontitis. In this study, we investigated the cooperative effects of Nel-like molecule type 1 (Nell-1) and gold nanoparticles (AuNPs) on macrophage polarization, osteoclast differentiation, and the corresponding functions in an experimental model of periodontitis in rats. Nell-1-combined AuNPs in in vitro studies were found to reduce the production of inflammatory factors (TNF-α, p < 0.0001; IL-6, p = 0.0012), modulate the ratio of M2/M1 macrophages by inducing macrophage polarization into the M2 phenotype, and inhibit cell fusion, maturation, and activity of osteoclasts. Furthermore, the local application of Nell-1-combined AuNPs in in vivo studies resulted in alleviation of damages to the periodontal and bone tissues, modulation of macrophage polarization and the activity of osteoclasts, and alteration of the periodontal microbiota, in which the relative abundance of the probiotic Bifidobacterium increased (p < 0.05). These findings reveal that Nell-1-combined AuNPs could be a promising drug candidate for the prevention and treatment of periodontitis. However, Nell-1-combined AuNPs did not show organ toxicity or impair the integrity of intestinal epithelium but alter the gut microbiota, leading to the dysbiosis of gut microbiota. The adverse impact of changes in gut microbiota needs to be further investigated. Nonetheless, this study provides a novel perspective and direction for the biological safety assessment of biomaterials in oral clinical applications.

An electrochemical biosensor for T4 polynucleotide kinase activity assay based on host-guest recognition between phosphate pillar[5]arene@MWCNTs and thionine.

T4 polynucleotide kinase helps with DNA recombination and repair. In this study, an electrochemical biosensor was developed for a T4 polynucleotide kinase activity assay and inhibitor screening based on phosphate pillar[5]arene and multi-walled carbon nanotube nanocomposites. The water-soluble pillar[5]arene was employed as the host to complex thionine guest molecules. The substrate DNA with a 5'-hydroxyl group initially self-assembled on the gold electrode surface through chemical adsorption of the thiol group, which was phosphorylated in the presence of T4 polynucleotide kinase. Titanium dioxide nanoparticles served as a bridge to link phosphorylated DNA and phosphate pillar[5]arene and multi-walled carbon nanotube composite due to strong phosphate-Ti4+-phosphate chemistry. Through supramolecular host-guest recognition, thionine molecules were able to penetrate the pillar[5]arene cavity, resulting in an enhanced electrochemical response signal. The electrochemical signal is proportional to the T4 polynucleotide kinase concentration in the range of 10-5 to 15 U mL-1 with a detection limit of 5 × 10-6 U mL-1. It was also effective in measuring HeLa cell lysate-related T4 polynucleotide kinase activity and inhibitor screening. The proposed method offers a unique sensing platform for kinase activity measurement, holding great potential in nucleotide kinase-target drug development, clinical diagnostics, and inhibitor screening.

A tuned triboelectric nanogenerator using a magnetic liquid for low-frequency vibration energy harvesting.

Wireless sensor networks have developed quickly in recent years, and the use of self-powered technology to replace traditional external power sources to power sensor nodes has become an urgent problem that needs to be solved. As an entirely novel type of self-powered technology, the triboelectric nanogenerator (TENG) has attracted widespread attention, but the inability to achieve adaptive adjustment based on the vibration environment has restricted the development of TENGs. Here, a magnetic liquid triboelectric nanogenerator (ML-TENG) is designed to harvest vibration energy to power sensing nodes, and ML-TENG tuning is achieved using a magnetic liquid to adapt to different vibration environments. The electrical performance of the ML-TENG was investigated by theoretical, experimental, and numerical research. According to the results, the developed ML-TENG responds well to low-frequency vibration, and the instantaneous power is up to 5.40 nW. The tuning function is achieved by adjusting the magnetic field, and the natural frequency can be adjusted between 6.6 Hz and 7.6 Hz. The strong linear connection between the output voltage of the ML-TENG and the external environment's vibration amplitude promotes the monitoring of the vibration environment and lays the groundwork for the creation of wireless sensor networks.

Inversion of magnetic diameter distribution of magnetic fluids under high and low temperatures.

The magnetic diameter is a crucial factor affecting the magnetic properties of magnetic fluids. The magnetic diameter distribution can be estimated based on the magnetic properties. However, the magnetic dipole interaction of magnetic nanoparticles (MNPs) and the variation of the magnetic diameter with temperature have received relatively little attention in previous research. Hence, this research proposes the AP-MMF1-L method to inverse the magnetic diameter which considers the magnetic dipole interaction and derives the magnetic diameter at different temperatures. Firstly, the AP-MMF1-L uses the least square method between the first-order modified mean-field Langevin function (MMF1-L) and the measured magnetization curve as the objective function. Meanwhile, the hybrid Artificial bee colony-particle swarm (AP) optimization algorithm is introduced to inverse the optimal magnetic diameter distribution. Secondly, the hydrodynamic diameter distribution experimental values are compared with the theoretical values, demonstrating the AP-MMF1-L method obtains accurate inversion results of the magnetic diameter distribution when compared to other models. Finally, the arithmetic mean of the magnetic diameter at different temperatures is investigated, revealing a decreasing trend as the temperature rises, approximately following a linear distribution. The AP-MMF1-L provides a novel and effective tool for accurately determining the magnetic diameter of the MNPs across various temperatures.

ZIF template-based Fe-doped defect-rich hierarchical structure Co3S4/MoS2 as a bifunctional electrocatalyst for overall water splitting.

To replace the current expensive precious metal catalysts for water electrolysis, it is important to develop inexpensive and powerful bifunctional catalysts for hydrogen production. It is an effective way to improve catalytic performance using excellent templates and elemental doping. Here, a hierarchical structure Fe-Co3S4/MoS2 was synthesized using an Fe-ZIF precursor prepared by ion exchange, followed by hydrothermal sulfuration and annealing. It required overpotentials of only 93 mV and 243 mV to achieve a current density of 10 mA cm-2 in the HER and OER, respectively. It also showed excellent catalytic performance for overall water splitting, requiring only 1.42 and 1.71 V to achieve current densities of 10 and 100 mA cm-2 in 1 M KOH. The catalyst also demonstrated excellent ultra-long-term stability. The superb catalytic performance and stability can be attributed to the Fe doping, exposing more active sites while retaining the highly stable framework of the ZIF. The component modulation of Co3S4 and MoS2 by Fe doping induced high intrinsic activity and excellent transfer coefficients. This work presents a novel approach to prepare noble metal-free catalysts with highly stable rich interfaces and defects for overall water splitting.

Formation of Molecular Junctions by Single-Entity Collision Electrochemistry.

Controlling and understanding the chemistry of molecular junctions is one of the major themes in various fields ranging from chemistry and nanotechnology to biotechnology and biology. Stochastic single-entity collision electrochemistry (SECE) provides powerful tools to study a single entity, such as single cells, single particles, and even single molecules, in a nanoconfined space. Molecular junctions formed by SECE collision show various potential applications in monitoring molecular dynamics with high spatial resolution and high temporal resolution and in feasible combination with hybrid techniques. This Perspective highlights the new breakthroughs, seminal studies, and trends in the area that have been most recently reported. In addition, future challenges for the study of molecular junction dynamics with SECE are discussed.

An electrochemical biosensor for T4 polynucleotide kinase activity identification according to host-guest recognition among phosphate pillar[5]arene@palladium nanoparticles@reduced graphene oxide nanocomposite and toluidine blue.

T4 polynucleotide kinase (T4 PNK) helps with DNA recombination and repair. In this work, a phosphate pillar[5]arene@palladium nanoparticles@reduced graphene oxide nanocomposite (PP5@PdNPs@rGO)-based electrochemical biosensor was created to identify T4 PNK activities. The PP5 used to complex toluidine blue (TB) guest molecules is water-soluble. With T4 PNK and ATP, the substrate DNA, which included a 5'-hydroxyl group, initially self-assembled over the gold electrode surface by chemical adsorption of the thiol units. Strong phosphate-Zr4+-phosphate chemistry allowed Zr4+ to act as a bridge between phosphorylated DNA and PP5@PdNPs@rGO. Through a supramolecular host-guest recognition connection, TB molecules were able to penetrate the PP5 cavity, where they produced a stronger electrochemical response. With a 5 × 10-7 U mL-1 detection limit, the electrochemical signal is linear in the 10-6 to 1 U mL-1 T4 PNK concentration range. It was also effective in measuring HeLa cell lysate-related PNK activities and screening PNK inhibitors. Nucleotide kinase-target drug development, clinical diagnostics, and screening for inhibitors all stand to benefit greatly from the suggested technology, which offers a unique sensing mechanism for kinase activity measurement.

A colorimetric and fluorometric dual-mode probe for Cu2+detection based on functionalized silver nanoparticles.

A novel colorimetric/fluorescent probe (AgNPs-GSH-Rh6G2) was prepared by linking silver nanoparticles (AgNPs) with rhodamine 6G derivative (Rh6G2) using glutathione (GSH) as a linker molecule. The prepared probe showed obvious fluorescence change and colorimetric response after adding copper ions. Based on this phenomenon, a colorimetric/fluorescence dual-mode detection method was constructed to recognize copper ions. The linear ranges of fluorescence detection and colorimetric detection were 0.10 to 0.45 mM and 0.15 to 0.65 mM, respectively, and the limit of detection were 0.18 µM and 24.90 µΜ. In addition, the dual-mode probe has achieved satisfactory results in the detection of copper ions in sediment samples. The successful construction of AgNPs-GSH-Rh6G2 not only provide a reliable tool for the detection of copper ions, but also shed light on a new idea for the multi-mode development of the detection platform.

A novel colorimetric/fluorescent dual-signal probe based on silver nanoparticles functionalized with L-cysteine and rhodamine 6G derivatives for copper ion detection and cell imaging.

The dual-signal probe utilizing functionalized silver nanoparticles (AgNPs) is a promising sensing tool. Herein, a novel colorimetric/fluorescent dual-signal probe (AgNPs-L-Cys-Rh6G2) was fabricated for copper ion (Cu2+) detection and cell imaging by using L-cysteine as a "bridge" to connect AgNPs and rhodamine 6G derivatives. The AgNPs-L-Cys-Rh6G2 probe exhibits a dual-signal response to Cu2+ due to Rh6G2 hydrolysis, resulting in a high fluorescence response and a significant change in color from light yellow to pink under sunlight. The linear detection ranges of the AgNPs-L-Cys-Rh6G2 probe for Cu2+ were 100-450 µM and 150-650 µM using fluorescent and colorimetry methods, respectively. The detection limits were as low as 0.169 µM and 1.36 µM, respectively. Meanwhile, the proposed probe was applied to detect Cu2+ in the actual sediment with satisfactory recovery and low relative standard deviation. Furthermore, the probe was further employed for fluorescence imaging in HeLa cells. In brief, the developed AgNPs-L-Cys-Rh6G2 sensing platform can be used for simultaneous Cu2+ determination and cell imaging.

Highly photoluminescent tryptophan-coated copper nanoclusters based turn-off fluorescent probe for determination of tetracyclines.

Employing cheap Cu nanoclusters to design a novel fluorescent probe have promising opportunities in the field of optical sensors. Here, we fabricated a highly photoluminescent D-tryptophan (D-Trp)-coated Cu nanoclusters (Trp-Cu NCs) by rapid microwave-assisted method to achieve precise quantification of tetracyclines (TC). Due to protecting groups of Trp, the synthesized Trp-Cu NCs have remarkable fluorescence stability with a quantum yield reached 12.5%. A distinct fluorescence quenching with the incremental addition of TC via the internal filtration effect (IFE). Based on turn-off fluorescence within 1 min, a detection method for detecting TC was constructed with a linear range of 0.3-120 µM and a limit of detection (LOD) of 0.12 µM. Besides, the proposed fluorescent probe has been employed for the determination of practical samples such as water samples, milk and honey, and exhibited satisfactory recoveries of 96.1%-108.2%, with relative standard deviations (RSD) lower than 5.0%. This is a sensitive, rapid and easily recognizable Trp-Cu NCs based sensing platform for the determination of TC, which could offer a powerful tool for ensuring food safety.

Charge transfer and vacancy engineering of Fe2O3 nanoparticle catalysts for highly selective N2 reduction towards NH3 synthesis.

The development of electrocatalysts for N2 reduction reaction (NRR) is significant for scalable and renewable NH3 synthesis, but calls for a technology innovation to overcome the specific problems of low efficiency and poor selectivity. Herein, we prepare a core-shell nanostructure by coating polypyrrole (PPy) onto sulfur-doped iron oxide nanoparticles (denoted as S-Fe2O3@PPy) as the highly selective and durable electrocatalysts for NRR under ambient conditions. Sulfur doping and PPy coating remarkably improve the charge transfer efficiency of S-Fe2O3@PPy, and the interactions between PPy and Fe2O3 nanoparticles produce abundant oxygen vacancies as active sites for NRR. This catalyst achieves an NH3 production rate of 22.1 µg h-1 mgcat-1 and a very-high Faradic efficiency of 24.6%, surpassing other Fe2O3 based NRR catalysts. Density functional theory calculations show that the S-coordinated iron site can successfully activate the N2 molecule and optimize the energy barrier during the reduction process, resulting in a small theoretical limiting potential.

Boosting Plant Photosynthesis with Carbon Dots: A Critical Review of Performance and Prospects.

Artificially augmented photosynthesis in nano-bionic plants requires tunable nano-antenna structures with physiochemical and optoelectronic properties, as well as unique light conversion capabilities. The use of nanomaterials to promote light capture across photosystems, primarily by carbon dots, has shown promising results in enhancing photosynthesis through tunable uptake, translocation, and biocompatibility. Carbon dots possess the ability to perform both down and up-light conversions, making them effective light promoters for harnessing solar energy beyond visible light wavelengths.This review presents and discusses the recent progress in fabrication, chemistry, and morphology, as well as other properties such as photoluminescence and energy conversion efficiency of nano-antennas based on carbon dots. The performance of artificially boosted photosynthesis is discussed and then correlated with the conversion properties of carbon dots and how they are applied to plant models. The challenges related to the nanomaterial delivery and the performance evaluation practices in modified photosystems, consideration of the reliability of this approach, and the potential avenues for performance improvements through other types of nano-antennas based on alternative nanomaterials are also critically evaluated. It is anticipated that this review will stimulate more high-quality research in plant nano-bionics and provide avenues to enhance photosynthesis for future agricultural applications.

Zr4+-mediated DNAzyme-driven DNA walker amplification strategy for electrochemical assay of protein kinase a activity and inhibition.

Protein kinase A (PKA) can regulate many cellular biological processes by phosphorylation substrate peptide or protein. Sensitive detection of PKA activity is critical for the PKA-related drug discovery and disease diagnosis. A new electrochemical biosensing method was developed for detection of PKA activity based on Zr4+-mediated DNAzyme-driven DNA walker signal amplification strategy. In this strategy, the special designed substrate peptide and a thiolated methylene blue-labeled hairpin DNA (MB-hpDNA) containing a single ribonucleic acid group (rA) could be anchored on the surface of gold electrode by Au-S bond. In the presence of adenosine triphosphate (ATP) and PKA, substrate peptide was phosphorylated and linked with walker DNA (WD) via the robust phosphate-Zr4+-phosphate chemistry. The linked WD hybridized with the loop region of MB-hpDNA to form a Mn2+-dependent deoxynuclease (DNAzyme), which cleaved the MB-hpDNA into MB-labeled fragment releasing away from electrode surface, resulting in a dramatic decrease of electrochemical signal and providing an electrochemical sensing platform for PKA activity detection. The response signal of the developed biosensor is proportional to the logarithm of PKA concentration in the range of 0.05 U mL-1 to 100 U mL-1, with a detection limit of 0.017 U mL-1 at a signal to noise ratio of 3. Furthermore, the proposed method can also be applied for the evaluation of PKA inhibition and PKA activity assay in cell samples. Therefore, the proposed biosensor shows great promise as a universal tool for diagnostics and drug discovery of PKA-related diseases.

In Situ Immobilization of Multi-Enzymes for Enhanced Substrate Channeling of Enzyme Cascade Reactions: A Nanoarchitectonics Approach by Directed Metal-Organic Frameworks.

Rationally tailoring a controlled spatial organization of enzymes in a nanoarchitecture for multi-enzyme cascade reactions can enhance the catalytic efficiency via substrate channeling. However, attaining substrate channeling is a grand challenge, requiring sophisticated techniques. Herein, we report facile polymer-directed metal-organic framework (MOF)-based nanoarchitechtonics for realizing a desirable enzyme architecture with significantly enhanced substrate channeling. The new method involves the use of poly(acrylamide-co-diallyldimethylammonium chloride) (PADD) as a modulator in a one-step process for simultaneous MOF synthesis and co-immobilization of enzymes (GOx and HRP). The resultant enzymes-PADD@MOFs constructs showed a closely packed nanoarchitecture with enhanced substrate channeling. A transient time close to 0 s was observed, owing to a short diffusion path for substrates in a 2D spindle-shaped structure and their direct transfer from one enzyme to another. This enzyme cascade reaction system showed a 3.5-fold increase in catalytic activity in comparison to free enzymes. The findings provide a new insight into using polymer-directed MOF-based enzyme nanoarchitectures to improve catalytic efficiency and selectivity.

Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic NbB Catalyst.

The ambient electrochemical N2 reduction reaction (NRR) is a future approach for the artificial NH3 synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber-Bosch technology. However, the challenge of N2 activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB2 nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH3 with a production rate of 30.5 µg h-1 mgcat -1 and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH3 production is attributed to the large amount of active B vacancies on the surface of NbB2 NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N2 on both unsaturated Nb and B atoms results in a significantly stretched N2 molecule. The weakened NN triple bonds are easier to be broken for a biased NH3 production. The diatomic catalysis is a future approach for NRR as it shows a special N2 adsorption mode that can be well engineered.