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Settling the structure stacking of graphene (G) nanosheets to maintain the high dispersity has been an intense issue to facilitate their practical application in the microelectronics-related devices. Herein, the co-doping of the highest electronegative fluorine (F) and large atomic radius chlorine (Cl) into G via a one-step electrochemical exfoliation protocol is engineered to actualize the ultralong cycling stability for flexible micro-supercapacitors (MSCs). Density functional theoretical calculations unveiled that the F into G can form the "ionic" C─F bond to increase the repulsive force between nanosheets, and the introduction of Cl can enlarge the layer spacing of G as well as increase active sites by accumulating the charge on pore defects. The co-doping of F and Cl generates the strong synergy to achieve high reversible capacitance and sturdy structure stability for G. The as-constructed aqueous gel-based MSC exhibited the superb cycling stability for 500,000 cycles with no capacitance loss and structure stacking. Furthermore, the ionic liquid gel-based MSC demonstrated a high energy density of 113.9 mW h cm-3 under high voltage of up to 3.5 V. The current work enlightens deep insights into the design and scalable preparation of high-performance co-doped G electrode candidate in the field of flexible microelectronics.

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Semitransparent solar cells are attracting attention not only for their visual effects but also for their ability to effectively utilize solar energy. Here, we demonstrate a translucent solar cell composed of bis(trifluoromethane sulfonyl)-amide (TFSA)-doped graphene (Gr), graphene quantum dots (GQDs), and LaVO3. By introducing a GQDs intermediate layer at the TFSA-Gr/LaVO3 interface, we can improve efficiency by preventing carrier recombination and promoting charge collection/separation in the device. As a result, the efficiency of the GQDs-based solar cell was 4.35%, which was higher than the 3.52% of the device without GQDs. Furthermore, the average visible transmittance of the device is 28%, making it suitable for translucent solar cells. The Al reflective mirror-based system improved the power conversion efficiency (PCE) by approximately 7% compared to a device without a mirror. Additionally, the thermal stability of the device remains at 90% even after 2000 h under an environment with a temperature of 60°C and 40% relative humidity. These results suggest that TFSA-Gr/GQDs/LaVO3-based cells have a high potential for practical use as a next-generation translucent solar energy power source.

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Bioelectricity generation by electrochemically active bacteria has become particularly appealing due to its vast potential in energy production, pollution treatment, and biosynthesis. However, developing high-performance anodes for bioelectricity generation remains a significant challenge. In this study, a highly efficient three-dimensional nitrogen-doped macroporous graphene aerogel anode with a nitrogen content of approximately 4.38 ± 0.50 at% was fabricated using hydrothermal method. The anode was successfully implemented in bioelectrochemical systems inoculated with Shewanella oneidensis MR-1, resulting in a significantly higher anodic current density (1.0 A/m2) compared to the control one. This enhancement was attributed to the greater biocapacity and improved extracellular electron transfer efficiency of the anode. Additionally, the N-doped aerogel anode demonstrated excellent performance in mixed-culture inoculated bioelectrochemical systems, achieving a high power density of 4.2 ± 0.2 W/m², one of the highest reported for three-dimensional carbon-based bioelectrochemical systems to date. Such improvements are likely due to the good biocompatibility of the N-doped aerogel anode, increased extracellular electron transfer efficiency at the bacteria/anode interface, and selectively enrichment of electroactive Geobacter soli within the NGA anode. Furthermore, based on gene-level Picrust2 prediction results, N-doping significantly upregulated the conductive pili-related genes of Geobacter in the three-dimensional anode, increasing the physical connection channels of bacteria, and thus strengthening the extracellular electron transfer process in Geobacter.

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The development of integrated analytical devices is crucial for advancing next-generation point-of-care platforms. Herein, we describe a facile synthesis of a strongly catalytic and durable Nitrogen-doped graphene oxide decorated platinum cobalt (NGO-PtCo) nanocomposite that is conjugated with target-specific DNA aptamer (i-e. MUC1) and grown on carbon fiber. Benefitting from the combined features of the high electrochemical surface area of N-doped GO, high capacitance and stabilization by Co, and high kinetic performance by Pt, a robust, multifunctional, and flexible nanotransducer surface was created. The designed platform was applied for the specific detection of a blood-based oncomarker, CA15-3. The electrochemical characterization proved that nanosurface provides a highly conductive and proficient immobilization support with a strong bio-affinity towards MUC1 aptamer. The specific interaction between CA15-3 and the aptamer alters the surface properties of the aptasensor and the electroactive signal probe generated a remarkable increase in signal intensity. The sensor exhibited a wide dynamic range of 5.0 × 10-2 -200 U mL-1, a low limit of detection (LOD) of 4.1 × 10-2 U mL-1, and good reproducibility. The analysis of spiked serum samples revealed outstanding recoveries of up to 100.03 %, by the proposed aptasensor. The aptasensor design opens new revelations in the reliable detection of tumor biomarkers for timely cancer diagnosis.

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Using nitrogen-doped graphene quantum dots (N-GQDs) and 3-aminophenylboronic acid (APBA), a novel fluorescence nanosensor was developed. This nanosensor exhibits high selectivity and sensitivity for lysine detection. Its sensing mechanism involves the suppression of electron transfer from APBA to the N-GQDs unit, thereby inhibiting photoinduced electron transfer and initiating internal charge transfer. At an optimal pH of 7, the protonated α-amine and ε-amine groups of lysine interact with the amide and boronic acid moieties, respectively. This interaction results in a redshift of fluorescence, substantially enhancing the response signal. A linear response was observed within a concentration range 0.40-3.01 µM, with the detection limit being 0.005 µM. A similar linear range was also achieved for the determination of lysine in human serum. Density functional theory calculations correlating molecular orbits and geometries support UV-vis and fluorescence findings. Additionally, the nanosensor was successfully applied to detect lysine in living cells and real samples, including milk and honey. For practical application, we construct a lysine-specific sensing platform using a commercial chip (TCS34725) that collects red, blue, and green signals, thereby facilitating the convenient use of the nanosensor. Overall, this study offers new perspectives on the development and application of fluorescent nanosensors for detecting individual amino acids.

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Levodopa, a widely prescribed drug in Parkinson's disease treatment, stands as the foremost prodrug of dopamine. An affordable self-testing kit is utilized to monitor  levodopa content in anti-parkinson drugs in human serum. A photoluminescent trinuclear Zn(II) complex [Zn3(L)2(κ1-OAc)2(κ2-OAc)2] has been synthesized, which cleaves into mononuclear  ZC in aqueous solution. ZC was found to detect L-Dopa in Tris-HCl buffer, exhibiting a moderate decrease in PL-emission. The real-life utility of the ZC probe is limited, for its lower sensitivity (LOD 35.3 µM) and separation challenges. Therefore, an interface between homogeneous and heterogeneous supports has been explored, leading to the strategic development of NGOZC, where ZC was grafted onto NGOQD. This material enables naked- eye detection under both ambient and UV light with color change from bright cyan to green, followed by dark. The nitrogen doping effect was investigated by several comparative investigations involving the synthesis of ZC-grafted GOQD, leading to enhanced quenching performance. Steady-state and time-resolved fluorescence titration study, morphological analysis, and computational calculations have been performed to get insights into the sensing mechanism. To the best of our knowledge, this as-synthesized NGOZC (LOD 1.78 nM) represents a promising strategy and platform for applications in biosensors, especially for Parkinson's and Alzheimer's diseases.

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Lithium (Li) metal has been regarded as the ideal anode for rechargeable batteries due to its low reduction potential and high theoretical capacity. However, the formation of fatal Li dendrites during repeated cycling shortens the battery life and causes serious safety concerns. Functionalized separators with electrically conductive and lithiophilic coating layers potentially inhibit dendrite formation and growth on Li metal anodes by providing nucleation sites for reversible Li deposition/stripping. In this work, we propose functionalized separators incorporating heteroatom-doped (N or B) graphene interlayers to modulate the Li nucleation behavior. The electronegative N-doping and electropositive B-doping were investigated to understand their regulation of the Li deposition behavior. With the heteroatom-doped graphene-coated separators, we observe significantly improved cycling stability along with enhanced charge transfer kinetics and low Li nucleation overpotential. This is attributed to the heteroatom-doped graphene interlayer expanding the surface area of the Li metal anode while providing additional space for uniform Li deposition/stripping, thus preventing undesirable side reactions. As a result, the formation of dendrites and pits on the Li metal anode surface is suppressed, demonstrating the protective effect of the Li metal anode. Interestingly, N-doped graphene-coated separators exhibit lower Li nucleation overpotentials than B-doped graphene-coated separators but rather lower average Coulombic efficiencies and reduced cycling stability. This implies that adequate adsorption on B-based sites, as opposed to the strong adsorption on N-based sites, improves the reversibility. Notably, the Li adsorption strength of the lithiophilic functional groups critically affects the reversibility, as observed by Li nucleation barrier measurements and atomistic simulations. This work suggests that interface engineering using conductive and lithiophilic materials can be a promising strategy for controlling Li deposition in advanced Li metal batteries.

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This work presents a hydrothermal method followed by a sonochemical treatment for synthesizing tantalum decorated on iron selenide (Ta/FeSe2) integrated with nitrogen-doped graphene (NGR) as a susceptible electrode material for detecting trolox (TRX) in berries samples. The surface morphology, structural characterizations, and electrochemical performances of the synthesized Ta/FeSe2/NGR composite were analyzed via spectrophotometric and voltammetry techniques. The GCE modified with Ta/FeSe2/NGR demonstrated an impressive linear range of 0.1 to 580.3 µM for TRX detection. Additionally, it achieved a remarkable limit of detection (LOD) of 0.059 µM, and it shows a high sensitivity of 2.266 µA µÐœ-1 cm-2. Here, we used density functional theory (DFT) to investigate the structures of TRX and TRX quinone and the locations of energy levels and electron transfer sites. The developed sensor exhibits significant selectivity, satisfactory cyclic and storage stability, and notable reproducibility. Moreover, the practicality of TRX was assessed in different types of berries, yielding satisfactory recoveries.

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Tyrosinase inhibitors have the ability to resist melanin formation and can be used for clinical and cosmetic, so it is becoming extremely crucial to search a rapid and effective method for detecting t the activity of tyrosinase. In this study, a sensing probe based on Nitrogen-doped graphene quantum dots (N-GQDs) were prepared with carbamide and citric acid. Tyrosinase can oxidize dopamine to dopamine quinone, which can quench the fluorescence of N-GQDs based on the principle of fluorescence resonance energy transfer (FRET) process, and then the detection of tyrosinase activity can be achieved. The result demonstrated that the fluorescence intensity of N-GQDs was a linear correlation with the activity of tyrosinase. Wide detection linear ranges between 0.05 and 5 U/mL and high selectivity. The detection range of tyrosinase was 0.05 to 5 U/mL and LOD of 0.005 U/mL. According to the above, the fluorescence method established in this work could be successfully used for the trace analysis of tyrosinase and it was verified that KA is an inhibitor of tyrosinase.

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Highly active catalysts with salt and acid/alkali resistance are desired in peroxymonosulfate (PMS) activation processes and marine environment applications. F- and Cl-doped graphene (F-GN and Cl-GN) were prepared via electronegative and atom radius adjustment for tetracycline hydrochloride (TCH) pollution removal to satisfy these requirements. The introduction of special F and Cl functionalities into graphene exhibits superior electron transfer properties for PMS activation, considering the experimental and density functional theory (DFT) calculation results. The TCH degradation efficiency reached up to 80% under various pH and salt disturbance conditions with F-GN and Cl-GN. Cl-GN exhibited an activity superior to F-GN due to the higher electron polarization effect of C atoms adjacent to Cl atoms. The presence of more positive charged C sites in Cl-GN (around Cl doping) is more favorable for PMS attachment and sequence radical generation than F-GN. In addition, the main active species functionalized during reaction included ·OH and SO4-·, and the stability of F-GN and Cl-GN was confirmed to be over 60% by recycle test. Final research results provide an effective strategy for designing and preparing PMS activators resistant to salt, acid, and alkali, thereby expanding their application potential.

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A magnetic molecularly imprinted polymer (MMIP) adsorbent incorporating amino-functionalized magnetite nanoparticles, nitrogen-doped graphene quantum dots and mesoporous carbon (MIP@MPC@N-GQDs@Fe3O4NH2) was fabricated to extract triazine herbicides from fruit juice. The embedded magnetite nanoparticles simplified the isolation of the adsorbent from the sample solution. The N-GQDs and MPC enhanced adsorption by affinity binding with triazines. The MIP layer provided highly specific recognition sites for the selective adsorption of three target triazines. The extracted triazines were determined by high-performance liquid chromatography (HPLC) coupled with diode-array detection (DAD). The developed method exhibited linearity from 1.5 to 100.0 µg L-1 with a detection limit of 0.5 µg L-1. Recoveries from spiked fruit juice samples were in the range of 80.1- 108.4 %, with a relative standard deviation of less than 6.0 %. The developed MMIP adsorbent demonstrated good selectivity, high extraction efficiency, ease of fabrication and use, and good stability.

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The quest for economically sustainable electrocatalysts to replace critical materials in anodes for the oxygen evolution reaction (OER) is a key goal in electrochemical conversion technologies, and, in this context, metal-organic frameworks (MOFs) offer great promise as alternative electroactive materials. In this study, a series of nanostructured electrocatalysts was successfully synthesized by growing tailored Ni-Fe-based MOFs on nitrogen-doped graphene, creating composite systems named MIL-NG-n. Their growth was tuned using a molecular modulator, revealing a non-trivial trend of the properties as a function of the modulator quantity. The most active material displayed an excellent OER performance characterized by a potential of 1.47 V (vs. RHE) to reach 10 mA cm-2, a low Tafel slope (42 mV dec-1), and a stability exceeding 18 h in 0.1 M KOH. This outstanding performance was attributed to the synergistic effect between the unique MOF architecture and N-doped graphene, enhancing the amount of active sites and the electron transfer. Compared to a simple mixture of MOFs and N-doped graphene or the deposition of Fe and Ni atoms on the N-doped graphene, these hybrid materials demonstrated a clearly superior OER performance.

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The current study explores the prospective of a nitrogen-doped graphene (NG) incorporated into ZnSe-TiO2 composites via hydrothermal method for supercapacitor electrodes. Structural, morphological, and electronic characterizations are conducted using XRD, SEM, Raman, and UV analyses. The electrochemical study is performed and galvanostatic charge-discharge (GCD) and cyclic voltammetry (CV) are evaluated for the supercapacitor electrode material. Results demonstrate improved performance in the ZnSe-NG-TiO2 composite, indicating its potential for advanced supercapacitors with enhanced efficiency, stability, and power density. Specific capacity calculations and galvanic charge-discharge experiments confirmed the promising electrochemical activity of ZnSe-NG-TiO2, which has a specific capacity of 222 C/g. The negative link among specific capacity and current density demonstrated the composite's potential for high energy density and high-power density electrochemical devices. Overall, the study shows that composite materials derived from multiple families can synergistically improve electrode characteristics for advanced energy storage applications.

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BACKGROUND: Presently, glyphosate (Gly) is the most extensively used herbicide globally, Nevertheless, its excessive usage has increased its accumulation in off-target locations, and aroused concerns for food and environmental safety. Commonly used detection methods, such as high-performance liquid chromatography and gas chromatography, have limitations due to expensive instruments, complex pre-processing steps, and inadequate sensitivity. Therefore, a facile, sensitive, and reliable Gly detection method should be developed. RESULTS: A photoelectrochemical (PEC) sensor consisting of a three-dimensional polymer phenylethnylcopper/nitrogen-doped graphene aerogel (PPhECu/3DNGA) electrode coupled with Fe3O4 NPs nanozyme was constructed for sensitive detection of Gly. The microscopic 3D network of electrodes offered fast transfer routes for photo-generated electrons and a large surface area for nanozyme loading, allowing high signal output and analytical sensitivity. Furthermore, the use of peroxidase-mimicking Fe3O4 NPs instead of natural enzyme improved the stability of the sensor against ambient temperature changes. Based on the inhibitory effect of Gly on the catalytic activity Fe3O4 NPs, the protocol achieved Gly detection in the range of 5 × 10-10 to 1 × 10-4 mol L-1. Additionally, feasibility of the detection was confirmed in real agricultural matrix including tea, maize seedlings, maize seeds and soil. SIGNIFICANCE: This work achieved facile, sensitive and reliable analysis towards Gly, and it was expected to inspire the design and utilization of 3D architectures in monitoring agricultural chemicals in food and environmental matrix.

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Bilayer graphene (Bl-Gr) and sulphur-doped graphene (S-Gr) have been integrated with LiTaO3 surface acustic wave (SAW) sensors to enhance the performance of NO2 detection at room temperature. The sensitivity of the Bl-Gr SAW sensors toward NO2, measured at room temperature, was 0.29º/ppm, with a limit of detection of 0.068 ppm. The S-Gr SAW sensors showed 0.19º/ppm sensitivity and a limit of detection of 0.140 ppm. The origin of these high sensitivities was attributed to the mass loading and elastic effects of the graphene-based sensing materials, with surface changes caused by the absorption of the NO2 molecules on the sensing films. Although there are no significant differences regarding the sensitivity and detection limit of the two types of sensors, the measurements in the presence of interferent gases and various humidity conditions outlined much better selectivity and sensing performances towards NO2 gas for the Bl-Gr SAW sensors.

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CONTEXT: To unravel the effects of the C vacancy, doping N type and number, the adsorption of HCHO and O2 was investigated on the graphene (Gr)-based supported Pt single atom by density functional theory calculations. The electronegativity of the vacancy and N-doped Gr was a crucial factor both for the anchoring for a Pt and the further adsorption of HCHO and O2 on the supported Pt. The electronegativity can be tuned by the C vacancy number (1V and 2V), the doping N type (graphitic-N, pyridinic-N and pyrrolic-N) and the doping pyridinic-N number (1N ~ 4N). The high electronegativity of the vacancy and N-doped Gr favored the anchoring for a Pt compared to the Gr, while too high electronegativity was detrimental for further adsorption of adsorbates on the supported Pt. The Bader charge analysis proved that the electronegativity followed the trend as pyrrolic-N > pyridinic-N > graphitic-N, and 4N-Gr > 2V-Gr > 3N-Gr > 2N-Gr > 1N-Gr > 1V-Gr > Gr. As a result, the pyridinic-N, the 1V-Gr, 1N-Gr and 2N-Gr with the suitable electronegativity achieved both stronger anchoring for a Pt and more favorable adsorption of HCHO and O2 on the supported Pt than the pristine Gr support. METHODS: Periodic DFT calculation was performed using the VASP code. The PAW method and the GGA-PBE functionals were used. Part of work was also carried out by the DSPAW procedure of Device Studio.

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The stability and reactivity of Pd4Ni4 and Pd4Cu4 clusters embedded on graphene modified by monovacancy and nitrogen doping were investigated using auxiliary density functional theory (ADFT) calculations. The most stable structure of the Pd4Ni4 cluster is found in high spin multiplicity, whereas the lowest stable energy structure of the Pd4Cu4 cluster is a close shell system. The interaction energies between the bimetallic clusters and the defective graphene systems are significantly higher than those reported in the literature for the Pd-based clusters deposited on pristine graphene. It is observed that the composites studied present a HOMO-LUMO gap less than 1 eV, which suggests that they may present a good chemical reactivity. Therefore, from the results obtained in this work it can be inferred that the single vacancy graphene and pyridinic N-doped graphene are potentially good support materials for Pd-based clusters.

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A novel electrochemical immunosensor for detecting potential depression biomarker Apolipoprotein A4 (Apo-A4) was developed using a multi-signal amplification approach. Firstly, the sensor utilized a modified electrode material, NG-PEI-COF, combining bipyridine-functionalized covalent organic framework (COF) and polyethyleneimine-functionalized nitrogen-doped graphene (NG-PEI), providing high surface area and excellent electron transfer capability for the first-stage amplification in electrical signal conduction. Subsequently, gold nanoparticles (AuNPs) were further electrodeposited onto the electrode, providing good biocompatibility and abundant binding sites for immobilizing the target antigen, thus achieving the second-stage amplification in target recognition and binding. To address the lack of redox properties of the antigen, a tracer probe was formed by loading AuNPs, anti-Apo-A4, and toluidine blue (TB) successively onto COF, leading to the third-stage amplification in signal conversion. The constructed electrochemical immunosensor TB/Ab/AuNPs/COF-Apo-A4/AuNPs/NG-PEI-COF/GCE exhibited excellent detection performance against Apo-A4 with a linear range of 0.01 to 300 ng mL-1 and had a low detection limit of 2.16 pg mL-1 (S/N = 3). In addition, the biosensor had good reproducibility (RSD = 2.31%), stability, and significant anti-interference performance toward other depression biomarkers. The sensor has been successfully used for the quantitative detection of Apo-A4 in serum, providing potential applications for detecting Apo-A4 in the clinic and serving as a reference for constructing sensing methods based on COF.

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The quest for efficient catalysts based on abundant elements that can promote the selective CO2 hydrogenation to green methanol still continues. Most of the reported catalysts are based on Cu/ZnO supported in inorganic oxides, with not much progress with respect to the benchmark Cu/ZnO/Al2O3 catalyst. The use of carbon supports for Cu/ZnO particles is much less explored in spite of the favorable strong metal support interaction that these doped carbons can establish. This manuscript reports the preparation of a series of Cu-ZnO@(N)C samples consisting of Cu/ZnO particles embedded within a N-doped graphitic carbon with a wide range of Cu/Zn atomic ratio. The preparation procedure relies on the transformation of chitosan, a biomass waste, into N-doped graphitic carbon by pyrolysis, which establishes a strong interaction with Cu nanoparticles (NPs) formed simultaneously by Cu2+ salt reduction during the graphitization. Zn2+ ions are subsequently added to the Cu-graphene material by impregnation. All the Cu/ZnO@(N)C samples promote methanol formation in the CO2 hydrogenation at temperatures from 200 to 300 °C, with the temperature increasing CO2 conversion and decreasing methanol selectivity. The best performing Cu-ZnO@(N)C sample achieves at 300 °C a CO2 conversion of 23% and a methanol selectivity of 21% that is among the highest reported, particularly for a carbon-based support. DFT calculations indicate the role of pyridinic N doping atoms stabilizing the Cu/ZnO NPs and supporting the formate pathway as the most likely reaction mechanism.

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To precise screening concentration of ascorbic acid (AA), a novel electrochemical sensor was prepared using palladium nanoparticles decorated on nitrogen-doped graphene quantum dot modified glassy carbon electrode (PdNPs@N-GQD/GCE). For this purpose, nitrogen doped GQD nanoparticles (N-GQD) were synthesized from a citric acid condensation reaction in the presence of ethylenediamine and subsequently modified by palladium nanoparticles (PdNPs). The electrochemical behavior of AA was investigated, in which the oxidation peak appeared at 0 V related to the AA oxidation. Considering the synergistic effect of Pd nanoparticles as an active electrocatalyst, and N-GQD as an electron transfer accelerator and electrocatalytic activity improving agent, PdNPs@N-GQD hybrid materials showed excellent activity in the direct oxidation of AA. In the optimal conditions, the voltammetric response was linear in the range from 30 to 700 nM and the detection limit was calculated to be 23 nM. The validity and the efficiency of the proposed sensor were successfully tested and confirmed by measuring AA in real samples of chewing tablets, and fruit juice.