Detection of Tyrosinase Activity and Inhibitor Validation Based on N-GQDs Fluorescence Sensor.

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.

A magnetic imprinted polymer nano-adsorbent with embedded quantum dots and mesoporous carbon for the microextraction of triazine herbicides.

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.

Utilization of Nitrogen-Doped Graphene Quantum Dots to Neutralize ROS and Modulate Intracellular Antioxidant Pathways to Improve Dry Eye Disease Therapy.

Purpose: Patients afflicted with dry eye disease (DED) experience significant discomfort. The underlying cause of DED is the excessive accumulation of ROS on the ocular surface. Here, we investigated the nitrogen doped-graphene quantum dots (NGQDs), known for their ROS-scavenging capabilities, as a treatment for DED. Methods: NGQDs were prepared by using citric acid and urea as precursors through hydrothermal method. The antioxidant abilities of NGQDs were evaluated through: scavenging the ROS both extracellular and intracellular, regulating the nuclear factor-erythroid 2-related factor (Nrf2) antioxidant pathway of human corneal epithelial cells (HCECs) and their transcription of inflammation related genes. Furthermore, NGQDs were modified by Arg-Gly-Asp-Ser (RGDS) peptides to obtain RGDS@NGQDs. In vivo, both the NGQDs and RGDS@NGQDs were suspended in 0.1% Pluronic F127 (w/v) and delivered as eye drops in the scopolamine hydrobromide-induced DED mouse model. Preclinical efficacy was compared to the healthy and DPBS treated DED mice. Results: These NGQDs demonstrated pronounced antioxidant properties, efficiently neutralizing free radicals and activating the intracellular Nrf2 pathway. In vitro studies revealed that treatment of H2O2-exposed HCECs with NGQDs induced a preservation in cell viability. Additionally, there was a reduction in the transcription of inflammation-associated genes. To prolong the corneal residence time of NGQDs, they were further modified with RGDS peptides and suspended in 0.1% Pluronic F127 (w/v) to create RGDS@NGQDs F127 eye drops. RGDS@NGQDs exhibited superior intracellular antioxidant activity even at low concentrations (10 µg/mL). Subsequent in vivo studies revealed that RGDS@NGQDs F127 eye drops notably mitigated the symptoms of DED mouse model, primarily by reducing ocular ROS levels. Conclusion: Our findings underscore the enhanced antioxidant benefits achieved by modifying GQDs through nitrogen doping and RGDS peptide tethering. Importantly, in a mouse model, our novel eye drops formulation effectively ameliorated DED symptoms, thereby representing a novel therapeutic pathway for DED management.

Fluorescence/electrochemical dual-mode strategy for Golgi protein 73 detection based on molybdenum disulfide/ferrocene/palladium nanoparticles and nitrogen-doped graphene quantum dots.

Golgi protein 73 (GP73) is a new serum marker associated with early diagnosis and postoperative assessment of hepatocellular carcinoma (HCC). Herein, an electrochemical/fluorescence dual-signal biosensor was designed for determination of GP73 based on molybdenum disulfide/ferrocene/palladium nanoparticles (MoS2-Fc-PdNPs) and nitrogen-doped graphene quantum dots (NGQDs). GP73 aptamer (Apt) was labeled with NGQDs to form the NGQDs-Apt fluorescence probe. MoS2-Fc-PdNPs served not only as the fluorescence quencher but also as electrochemical enhancer. The sensing platform (NGQDs-Apt/MoS2-Fc-PdNPs) was formed based on the fluorescence resonance energy transfer (FRET) mechanism. In the presence of GP73, the specific binding of NGQDs-Apt to GP73 interrupted FRET, restoring the fluorescence of NGQDs-Apt at λex/em = 348/438 nm and enhancing the oxidation current of Fc in MoS2-Fc-PdNPs at 0.04 V through differential pulse voltammetry (DPV). Under the optimal conditions, the DPV current change and fluorescence recovery have a good linear relationship with GP73 concentration from 1.00 to 10.0 ng/mL. The calibration equation for the fluorescence mode was Y1 = (0.0213 ± 0.00127)X + (0.0641 ± 0.00448) and LOD was 0.812 ng/mL (S/N = 3). The calibration equation of the electrochemical mode was Y2 = (3.41 ± 0.111)X + (1.62 ± 0.731), and LOD of 0.0425 ng/mL (S/N = 3). The RSDs of fluorescence mode and electrochemical mode after serum detection were 1.62 to 5.21% and 0.180 to 6.62%, respectively. By combining the electrochemical and fluorescence assay, more comprehensive and valuable information for GP73 was provided. Such dual-mode detection platform shows excellent reproducibility, stability, and selectivity and has great application potential.

Plasma-Enabled Graphene Quantum Dot Hydrogel-Magnesium Composites as Bioactive Scaffolds for In Vivo Bone Defect Repair.

Bioactive and mechanically stable metal-based scaffolds are commonly used for bone defect repair. However, conventional metal-based scaffolds induce nonuniform cell growth, limiting damaged tissue restoration. Here, we develop a plasma nanotechnology-enhanced graphene quantum dot (GQD) hydrogel-magnesium (Mg) composite scaffold for functional bone defect repair by integrating a bioresource-derived nitrogen-doped GQD (NGQD) hydrogel into the Mg ZK60 alloy. Each scaffold component brings major synergistic advantages over the current alloy-based state of the art, including (1) mechanical support of the cortical bone and calcium deposition by the released Mg2+ during degradation; (2) enhanced uptake, migration, and distribution of osteoblasts by the porous hydrogel; and (3) improved osteoblast adhesion and proliferation, osteogenesis, and mineralization by the NGQDs in the hydrogel. Through an in vivo study, the hybrid scaffold with the much enhanced osteogenic ability induced by the above synergy promotes a more rapid, uniform, and directional bone growth across the hydrogel channel, compared with the control Mg-based scaffold. This work provides insights into the design of multifunctional hybrid scaffolds, which can be applied in other areas well beyond the demonstrated bone defect repair.

A novel fluorescent strategy for Golgi protein 73 determination based on aptamer/nitrogen-doped graphene quantum dots/molybdenum disulfide @ reduced graphene oxide nanosheets.

The effective detection of biomarkers associated with hepatocellular carcinoma (HCC) is of great importance. Golgi protein 73 (GP73), a serum biomarker of HCC, has better diagnostic value than Alpha-fetoprotein (AFP) has been reported. In this paper, highly accurate fluorescence sensing platform for detecting GP73 was constructed based on fluorescence resonance energy transfer (FRET), in which nitrogen-doped graphene quantum dots (NGQDs) labelling with GP73 aptamer (GP73Apt) was used as fluorescence probe, and molybdenum disulfide @ reduced graphene oxide (MoS2@RGO) nanosheets was used as fluorescent receptors. MoS2@RGO nanosheets can quench the fluorescence of NGQDs-GP73Apt owing to FRET mechanisms. In the presence of GP73, the NGQDs-GP73Apt specifically bound with GP73 to from the deployable structures, making NGQDs-GP73Apt far away from MoS2@RGO nanosheets, blocking the FRET process, resulting in fluorescence recovery of NGQDs-GP73Apt. Under optimal conditions, the recovery intensity of fluorescence in the detection system is linearly related to the concentration of GP73 in the range of 5 ng/mL - 100 ng/mL and the limit of detection is 4.54 ng/mL (S/N = 3). Moreover, detection of GP73 was performed in human serum samples with good recovery (97.21-100.83%). This platform provides a feasible method for the early diagnosis of HCC, and can be easily extended to the detection of other biomarkers.

Fabrication of nitrogen-doped graphene quantum dots based fluorescent probe and its application for simultaneous, sensitive and selective detection of umami amino acids.

In this work, nitrogen-doped graphene quantum dots (N-GQDs) were synthesized by an efficient one-step hydrothermal using hydrated citric acid and urea as the carbon and nitrogen sources, respectively. The fluorescent quantum yield of the N-GQDs was up to 88.20 %, and the fluorescence lifetime was 12.29 ns. Based on the excellent fluorescence property, water-soluble and low cytotoxicity of N-GQDs, a novel fluorescent probe was fabricated and used for simultaneous detection of l-glutamic acid (l-Glu) and l-aspartic acid (l-Asp). Herein, Al3+ was used as a chelant agent for l-Glu shielding. The sensitive response of the probe towards l-Glu and l-Asp presented a wide concentration range with a low detection limit (S/N = 3). The fluorescent probe showed good selectivity, high stability and acceptable reproducibility in the application of l-Glu/l-Asp simultaneous detection in chicken soup. Meanwhile, the detection results of the fluorescent probe were correlated well with those obtained by amino acid analyzer.

Fluorescent "turn-on" aptamer sensor for sensitive and reliable detection of Golgi glycoprotein 73 based on nitrogen-doped graphene quantum dots and molybdenum disulfide nanosheets.

The sensitivity and specificity of Golgi glycoprotein 73 (GP73) are very important for early diagnosis of hepatocellular carcinoma. Herein, we constructed a new-fashioned fluorescent aptamer sensor for GP73 determination based on nitrogen-doped graphene quantum dots (N-GQDS) and molybdenum disulfide (MoS2) nanosheets. N-GQDs with high fluorescence intensity and good stability were screened out, and GP73 aptamer (GP73Apt) is labeled with N-GQDs to form the N-GQDs-GP73Apt fluorescence probe. MoS2 nanosheets can quench the fluorescence of N-GQDs-GP73Apt owing to fluorescence resonance energy transfer mechanisms. After introducing GP73 into the biosensing system, the N-GQDs-GP73Apt specifically bound with GP73 to form the deployable structures, making N-GQDs-GP73Apt far away from MoS2, blocking the fluorescence energy transfer process, and restoring the fluorescence of N-GQDs-GP73Apt. When the GP73 concentration was in the extent of 2.5 ng/mL∼100 ng/mL, the relative fluorescence recovery is linearly relevant to the concentration of GP73, and the limit of detection (LOD) was 1.29 ng/mL (S/N = 3). Moreover in the application of actual serum sample detection, the recovery was range 98.85∼100.55 %. The fluorescent aptamer sensor can rapidly detect and analyze the serum marker GP73 with the characteristics of low-cost, high sensitivity, good specificity and recovery.

One-step preparation of N-doped grapheme quantum dots with high quantum yield for bioimaging and highly sensitive electrochemical detection of isoniazid.

Conventional techniques for synthesizing GQDs have a poor quantum yield (QY) that restricts their biological applications. Herein, we present a rapid, cost-effective and high quantum yield synthesis of nitrogen-doped graphene quantum dots (N-GQDs) through a scientific microwave reactor. The reaction parameters like microwave irradiation time, temperature, precursor concentration and pressure were optimized for achieving high quantum yield. The prepared N-GQDs exhibit bright blue fluorescence and excitation independent emission property with a quantum yield of 42.81%. In-vivo investigations on C. elegans revealed that the as-prepared N-GQDs are exceptionally biocompatible and maintain the normal physiological functioning of the primary and secondary targeted organs in nematodes. The synergetic effect of intestinal barrier and defecation behavior mitigates N-GQDs translocation into reproductive organs of nematode. In addition, the N-GQDs modified GCE was tested for electrochemical sensing characteristics towards the anti-tuberculosis drug isoniazid (INZ). The N-GQDs showed appreciable electrocatalytic performance towards INZ with high sensitivity (3.76 µA µM-1 cm-1). The differential pulse voltammetry (DPV) analysis of N-GQDs exhibit a lower detection limit of 10.91 nM for INZ. The N-GQDs modified sensor exhibits good reproducibility, excellent anti-interference ability and excellent analytical performance for INZ in real samples like human blood serum and urine samples.

A robust electrochemical sensing platform for the detection of erlotinib based on nitrogen-doped graphene quantum dots/copper nanoparticles-polyaniline-graphene oxide nanohybrid.

Erlotinib is a potent and highly specific tyrosine kinase inhibitor with the hindering effects on the growth of cancer cells. An electrochemical sensor with the great sensitivity and selectivity was fabricated for determining erlotinib by using a graphite rod electrode modified by the nitrogen-doped graphene quantum dots (N-GQDs) and a ternary nanohybrid comprising copper nanoparticles, polyaniline, along with graphene oxide (N-GQDs/CuNPs-PANI@GO) for the first time. The establishment of PANI and CuNPs was done simultaneously on the GO surface by thein situoxidative polymerization method. The morphological characteristics and elemental structure of the synthesized nanoparticles were examined by some microscopy techniques and x-ray energy/diffraction methods. The fabricated sensor represented the electrocatalytic activity towards erlotinib with a linear detection range from 1.0 nM to 35.0µM, a detection limit of 0.712 nM, and a sensitivity of 1.3604µAµM-1. Moreover, the N-GQDs/CuNPs-PANI@GO sensor showed acceptable stability up to 30 d (94.82%), reproducibility (RSD values of 3.19% intraday and 3.52% interday), and repeatability (RSD value of 3.65%) as a novel and powerful electrochemical sensor. It was successfully applied to monitor erlotinib in the drug-injected aqueous solution, serum, and urine samples that proved the capability of the sensor for the erlotinib monitoring in the biological samples.

Quantifying H2O2 by ratiometric fluorescence sensor platform of N-GQDs/rhodamine B in the presence of thioglycolic acid under the catalysis of Fe3.

In the presence of thioglycolic acid (TGA) and under the catalysis of Fe3+, a simple, rapid, sensitive, selective and effective ratiometric fluorescence sensor platform based on the mixed physically blue nitrogen-doped graphene quantum dots (N-GQDs) as probe signals and orange rhodamine B as internal standard signals has been constructed for analysis of H2O2 in human serum. TGA is the key factor for fluorescence response toward H2O2 by N-GQDs and the mechanism is H2O2 reacts speedily with TGA under the catalysis of Fe3+, and produces intermediate of superoxide anions (O2-), which accepts electrons from N-GQDs, and generates graphene oxide, causing the fluorescence quench of N-GQDs. Compared with N-GQDs probe, the sensitivity of the ratiometric fluorescence sensor platform of N-GQDs/rhodamine B for analysis of H2O2 has been improved by nearly 5-folds. Under the optimum conditions, Fλ=580nm/Fλ=440nm has a good linear relationship with the concentration of H2O2 and the detection limit of H2O2 is 0.46 µmol/L with 3.5% RSD. The established sensor platform has been successfully used for probing H2O2 in human serum with satisfactory results. The superior performance of the probe lies in its high selectivity and can be directly employed in detecting H2O2 in serum samples without any sample pretreatment procedures.

Sensitive and Selective Detection of Clenbuterol in Meat Samples by a Graphene Quantum Dot Fluorescent Probe Based on Cationic-Etherified Starch.

The use of clenbuterol (CLB) in large quantities in feedstuffs worldwide is illegal and potentially dangerous for human health. In this study, we directly prepared nitrogen-doped graphene quantum dots (N-GQDs) by a one-step method using cationic-etherified starch as raw material without pollution, which has the advantages of simple, green, and rapid synthesis of N-GQDs and high doping efficiency of nitrogen elements, compared with the traditional nitrogen doping method of reacting nitrogen source raw material with quantum dots. The N-GQDs synthesized by cationic etherification starch with different substitution degrees (DSs) exhibit good blue-green photoluminescence, good fluorescence stability, and water solubility. By comparing the fluorescence emission intensity of the two methods, the N-GQDs prepared by this method have higher fluorescence emission intensity and good fluorescence stability. Based on the static quenching mechanism between CLB and N-GQDs, a fluorescent probe was designed to detect CLB, which exhibited a wide linear range in the concentration range of 5 × 10-10~5 × 10-7 M (R2 = 0.9879) with a limit of detection (LOD) of 2.083 × 10-13 M. More excitingly, the N-GQDs fluorescent probe exhibited a satisfactory high selectivity. Meanwhile, it can be used for the detection of CLB in chicken and beef, and good recoveries were obtained. In summary, the strategic approach in this paper has potential applications in the detection of risky substances in the field of food safety.

Sensitive detection of trace level Cd (II) triggered by chelation enhanced fluorescence (CHEF) "turn on": Nitrogen-doped graphene quantum dots (N-GQDs) as fluorometric paper-based sensor.

Cadmium ion (Cd (II)) is a highly toxic heavy metal usually found in natural water. Exposure to Cd (II) can produce serious effects in human organs such as Itai-Itai disease. Therefore, the maximum allowance levels of Cd (II) in drinking water and herbal medicines imposed by the World Health Organization (WHO) are 3 µg L-1 and 300 µg kg-1, respectively. In this work, nitrogen-doped graphene quantum dots (N-GQDs) as a fluorescent sensor for Cd (II) determination was developed in both solution-based and paper-based systems. N-GQDs were synthesized from citric acid (CA) and ethylenediamine (EDA) via the hydrothermal method. The synthesized N-GQDs emitted intense blue fluorescence with a quantum yield (QY) of up to 80%. The functional groups on the surface of N-GQDs measured by FTIR were carboxyl (COO-), hydroxyl (OH-), and amine (NH2) groups, suggesting that they could be bound to Cd (II) for complexation. The fluorescence intensity of N-GQDs was gradually enhanced with the increase of Cd (II) concentration. This phenomenon was proved to result from the fluorescence enhancement (turn-on) based on the chelation enhanced fluorescence (CHEF) mechanism. Under the optimum conditions in the solution-based and paper-based systems, the limits of detection (LODs) were found to be 1.09 and 0.59 µg L-1, respectively. Furthermore, the developed sensors showed relatively high selectivity toward Cd (II) over ten other metal cations and six other anions of different charges. The performance of the sensor in real water and herbal medicine samples exhibited no significant difference as compared to the results of the validation method (ICP-OES). Therefore, the developed sensors can be used as fluorescent sensors for Cd (II) determination with high sensitivity, high selectivity, short incubation time (5 min). As such, the paper-based strategy has excellent promising potential for practical analysis of Cd (II) in water and herbal medicine samples with a trace level of Cd (II) concentrations.

Microplasma Band Structure Engineering in Graphene Quantum Dots for Sensitive and Wide-Range pH Sensing.

pH sensing using active nanomaterials is promising in many fields ranging from chemical reactions to biochemistry, biomedicine, and environmental safety especially in the nanoscale. However, it is still challenging to achieve nanotechnology-enhanced rapid, sensitive, and quantitative pH detection with stable, biocompatible, and cost-effective materials. Here, we report a rational design of nitrogen-doped graphene quantum dot (NGQD)-based pH sensors by boosting the NGQD pH sensing properties via microplasma-enabled band-structure engineering. Effectively and economically, the emission-tunable NGQDs can be synthesized from earth-abundant chitosan biomass precursor by controlling the microplasma chemistry under ambient conditions. Advanced spectroscopy measurements and density functional theory (DFT) calculations reveal that functionality-tuned NGQDs with enriched -OH functional groups and stable and large Stokes shift along the variations of pH value can achieve rapid, label-free, and ionic-stable pH sensing with a wide sensing range from pH 1.8 to 13.6. The underlying mechanism of pH sensing is related to the protonation/deprotonation of -OH group of NGQDs, leading to the maximum pH-dependent luminescence peak shift along with the bandgap broadening or narrowing. In just 1 h, a single microplasma jet can produce a stable colloidal NGQD dispersion with 10 mg/mL concentration lasting for at least 100 pH detections, and the process is scalable. This approach is generic and opens new avenues for nanographene-based materials synthesis for applications in sensing, nanocatalysis, energy generation and conversion, quantum optoelectronics, bioimaging, and drug delivery.

Synergistic Effect in a Graphene Quantum Dot-Enabled Luminescent Skinlike Copolymer for Long-Term pH Detection.

The alluring properties of a luminescent graphene quantum dot (GQD)-based nanocomposite are unquestionable to realize many advanced applications, such as sweat pH sensors. The well-suited hydrophilic polymers to host GQDs can face an unavoidable swelling behavior, which deteriorates the mechanical stability, whereas the hydrophobic polymers can prevent swelling but at the same time barricade the analyte pathways to GQDs. To resolve the two aforementioned obstacles, we develop a nanocomposite film containing nitrogen-doped GQDs (NGQDs) incorporated into a transparent, elastic, and self-healable polymer matrix, composed of a hydrophobic n-butyl acrylate segment and a hydrophilic N-(hydroxymethyl)acrylamide segment for wearable healthcare pH sensors on the human body. Besides serving as the fluorescence source, NGQDs are also designed as a nano-cross-linker to promote abundant chemical and physical interactions within the nanocomposite network. This synergetic effect gives rise to a 10-fold higher mechanical strength, 7-fold increment in Young's modulus, 4-fold increment in toughness, and 15-fold more sensitivity in pH detection (pH 3-10) compared to those of the pristine copolymer and NGQDs, respectively. Moreover, the mechanically enhanced nanocomposite possesses a high self-healing efficiency (94%) at room temperature even under water and demonstrates a stable sensing performance after repetitive usage for 30 days. Our work provides insights into the simple preparation of human skinlike nanocomposite elastomers usable for wearable pH sensors.

One-Pot Synthesis of Bright Blue Luminescent N-Doped GQDs: Optical Properties and Cell Imaging.

High fluorescent graphene quantum dots (GQDs) are promising in bioimaging and optoelectronics. In this paper, bright blue fluorescent N-doped GQDs were synthesized using a ultrasonic-assisted hydrothermal method. The morphology, structure, surface chemistry, optical properties, and stability subject to photo-bleaching, temperature, pH and preservation period for the N-GQDs were investigated in detail using various microscopy and spectroscopy techniques. The results showed that the N-GQDs possessed an average size of 2.65 nm, 3.57% N doping, and up to 54% quantum yield (QY). The photoluminescence (PL) spectra of the N-GQDs are excitation dependent when excited in the range of 300-370 nm and excitation independent in the range of 380-500 nm for the core and surface states emission. The N-GQDs showed excellent photo-bleaching resistance and superior photo-stability. At room temperature and in the pH range of 3-8, the fluorescence of the N-GQDs was almost invariable. The N-GQDs can be stably preserved for at least 40 days. The average decay lifetime of the N-GQDs was 2.653 ns, and the radiative and nonradiative decay rate constants were calculated to be 2.04 × 108 s-1 and 1.73 × 108 s-1, respectively. The PL mechanism was qualitatively explained. The N-GQDs was used for cell imaging, and it showed good results, implying great potential applications for bioimaging or biomarking.

Microplasma-Tunable Graphene Quantum Dots for Ultrasensitive and Selective Detection of Cancer and Neurotransmitter Biomarkers.

The effective and precise detection of cancer and neurotransmitter biomarkers including folic acid (FA), dopamine (DA), and epinephrine (EP) are essential for early detection and diagnosis of cancer and neurological disorders and for the development of new drugs. However, it remains challenging to detect FA, DA, and EP with high selectivity and sensitivity with a single material. Herein, we report a photoluminescence (PL)-based selective sensing of FA, DA, and EP with nitrogen-doped graphene quantum dots (NGQDs) synthesized from biocompatible chitosan under ambient conditions using atmospheric pressure microplasmas. By regulating the pH, the selective detection is achieved in broad ranges from 0.8 to 80 µM for FA and 0.4 to 100 µM for both DA and EP with the very low limits of detections of 81.7, 57.8, and 16.7 nM for FA, DA, and EP, respectively. The developed PL sensing method shows the high throughput of 5000 detections per hour. Moreover, highly stable colloidal NGQD dispersion with 100 µg/mL concentration for at least 100 PL detections is produced in 1 h by a single microplasma, and the process is scalable. The mechanisms of the outstanding performance are related to the enhanced, size-dependent π-π stacking attraction between the NGQDs and the pH-regulated chemical states of the analytes and the associated pH-specific photo-induced electron transfer and PL.

Hyaluronic acid conjugated nitrogen-doped graphene quantum dots for identification of human breast cancer cells.

Accurate distinguish of cancer cells through fluorescence plays an important role in cancer diagnosis. Here we synthesized a blue fluorescent nitrogen-doped graphene quantum dots (N-GQDs) from citric acid and diethylamine via one-step hydrothermal synthesis method which was simple and quick to avoid by-products, and highlighted the binding sites to achieve precise combination. Due to the nitrogen element doping, amide II bond was amply obtained and abundant binding sites were provided for hyaluronic acid (HA) conjugation. N-GQDs solution with different pH value was then conjugated to HA via an amide bond for the recognition of human breast cancer cells (MCF-7 cells), and the formation of amide bond was more favorable under alkaline conditions. HA conjugated N-GQDs (HA-N-GQDs) were combined with CD44 which was over expressed on the surface of MCF-7 cells, resulting in MCF-7 cells performing stronger fluorescence. HA-N-GQDs showed high fluorescence, low toxicity, and good cytocompatibility, which held it play a role in fluorescence imaging for accurate identification of cancer cells.

Monitoring the mechanism of anti-cancer agents to inhibit colorectal cancer cell proliferation: Enzymatic biosensing of glucose combined with molecular docking.

Glucose, a major energy source in cellular metabolism, has a significant role in cell growth. The increase in glucose uptake is a distinguishing hallmark in cancer cells. A key step in glucose utilization is the transport of glucose to the cancer cells for supplying their additional energy. The glucose transporter (or GLUT) family is a membrane protein which facilitates the uptake of glucose in most cancer cell types. Given the increased glucose level in cancer cells and the regulatory role of GLUTs in glucose uptake, it is required to combine both experimental and theoretical studies to develop new methods to monitor cell proliferation. Herein, for the first time, a new strategy was proposed to evaluate the cell proliferation of HT-29 based on glucose consumption in the presence of resveratrol (RSV) as an anticancer agent. A hybrid nanocomposite of carbon nanofibers and nitrogen-doped graphene quantum dots was used to design an enzymatic sensor for the selective and sensitive determination of glucose in cancer cells. The results obtained from the voltammetric technique were compared with the conventional colorimetric assay. A good correlation was observed between the proliferation rate and glucose utilization by cancer cells. As it was observed, RSV induces a decrease in glucose consumption, indicating lower glucose uptake efficiency for HT-29 cells. Molecular docking studies reveal that RSV can block the interaction of glucose with the GLUT family. This is one of the possible mechanisms for the decrease of glucose level followed by the reduction of cell proliferation in the presence of RSV. Compared with traditional methods, in vitro electrochemical techniques benefit from simple, nontoxic, sensitive and low-cost detection assays and hence serve as a novel tool to pursue the growth inhibition of cancer cell in response to anti-cancer agents.

Ultra-sensitive photoelectrochemical aptamer biosensor for detecting E. coli O157:H7 based on nonmetallic plasmonic two-dimensional hydrated defective tungsten oxide nanosheets coupling with nitrogen-doped graphene quantum dots (dWO3•H2O@N-GQDs).

Light absorption and interfacial engineering of photoactive materials play vital roles in photoexcited electron generation and electron transport, and ultimately boost the performance of photoelectrochemical (PEC) biosensing. In this work, a novel high-performance photoelectrochemical (PEC) biosensing platform was fabricated based on nonmetallic plasmonic tungsten oxide hydrate nanosheets (WO3•H2O) coupling with nitrogen doped graphene quantum dots (N-GQDs) by a facile one-step hydrothermal approach. The localized surface plasmon resonance (LSPR) properties were achieved by oxygen vacancy engineered WO3·H2O (dWO3•H2O), which could greatly extend the light absorption from visible light to near-infrared light. Moreover, by coupling with N-GQDs, the as-fabricated heterojunction (dWO3•H2O@N-GQD) provided a much enhanced photoelectric response due to the efficient charge transfer. By conjugation with E.coli O157:H7 aptamer, a novel PEC aptasensor based on dWO3•H2O@N-GQD heterojunction was fabricated with a high sensitivity for detection of E.coli O157:H7. The limit of detection (LOD) of this PEC aptasensor is 0.05 CFU/mL with a linear detection range from 0.1 to 104 CFU/mL. Moreover, high reproducibility and good accuracy could also be achieved for analysis in milk samples. This work could provide a promising platform for the development of PEC bioanalysis and offer an insight into the non-metallic plasmonic materials based heterojunctions for high-performances PEC biosensing.