Wireless Gold/Boron-Nitrogen-Codoped Graphene-Based Antenna Immunosensor for the Rapid Detection of Neuron-Specific Enolase.

Tumor-marker immunosensors for rapid on-site detection have not yet been developed because of immunoreaction bottlenecks, such as shortening the reaction time and facilitating incubation. In this study, a gold-boron-nitrogen-codoped graphene (Au-BNG)-based immunosensor antenna was constructed for the rapid detection of neuron-specific enolase (NSE). A Au-BNG radiation electrode with dual functions of antibody protein fixation and signal transmission was developed for the first time. A radiation sample cell was constructed by embedding a radiation electrode into the groove of a poly(dimethylsiloxane) dielectric substrate. The constructed sense antenna achieves accurate detection of NSE with a range from 50 fg mL-1 to 40,000 pg mL-1 and a limit of detection of 10.99 fg mL-1, demonstrating excellent selectivity, stability, and reliability. The tumor-marker detection meter can provide NSE detection results as rapidly as within 2 min by using the new strategy of the microwave self-incubation of tumor markers. This antenna immunosensor is suitable for rapid detection in outpatient clinics and can be developed into household tumor-marker detectors, which would be significant in the early detection, long-term monitoring, and efficacy evaluation of tumors.

A label-free electrochemical immunosensor based on a gold-vertical graphene/TiO2 nanotube electrode for CA125 detection in oxidation/reduction dual channels.

A label-free immunosensor was constructed in oxidation and reduction dual channel mode for the trace detection of cancer antigen 125 (CA125) in serum. The gold-vertical graphene/titanium dioxide (Au-VG/TiO2) electrode was used as the signal-amplification platform, and cytosine and dopamine were used as probes in the oxidation and reduction channels, respectively. VG nanosheets were synthesized on a TiO2 nanotube array via chemical vapor deposition (CVD), and Au nanoparticles were deeply embedded on the surface and in the root of the VG nanosheets via electrodeposition. The CA125 antibody was then directly immobilized onto the electrode surface, benefitting from its natural affinity for Au nanoparticles. In the oxidation and reduction channels the CA125 antibody-Au-VG/TiO2 immune electrode had the same response concentration range (0.01-1000 mU∙mL-1) for the determination of the CA125 antigen. However, the oxidation channel had a higher sensitivity (14.82 µA•(log(mU•mL-1))-1 at a working potential of ~ 1.25 V vs. SCE), lower detection limit (0.0001 mU∙mL-1), higher stability, and lower performance deviation than the reduction channel. This immunosensor was successfully used for CA125 detection in human serum. The recoveries of spiked serum samples ranged from 99.8 ± 0.5 to 100 ± 0.4%. The study on the difference in the sensing performance between oxidation and reduction channels provides a preliminary experimental reference for exploring dual-channel synchronous detection immunosensors and verifying the accuracy of the assay based on dual-channel data, which will promote the development of reliable electrochemical immunosensor technology.

Electrochemical needle sensor based on a B, N co-doped graphene microelectrode array for the on-site detection of salicylic acid in fruits and vegetables.

In this study, a microelectrode array sensor based on boron and nitrogen co-doped vertical graphene (BNVG) was assembled to quantify salicylic acid (SA) in living plants. The influence of B and N contents on the electrochemical reaction kinetics and SA response signal was investigated. A microneedle sensor with three optimized BNVG microelectrodes (3.57 at.% B and 3.27 at.% N) was used to quantitatively analyze SA in the 0.5-100 µM concentration range and pH 4.0-9.0, with limits of detection of 0.14-0.18 µM. Additionally, a quantitative electrochemical model database based on the BNVG microelectrode sensor was constructed to monitor the growth of cucumbers and cauliflowers, which confirmed that the SA level and plant growth rate were positively correlated. Moreover, the SA levels in various vegetables and fruits purchased from the market were measured to demonstrate the practical application prospects for on-site inspection and evaluation.

Two-channel electrochemical immunosensor based on one-step-synthesized AuPt-boron-doped graphene electrode for CA153 detection.

Herein, a novel dual-channel electrochemical immunosensor was fabricated via vertical growth of AuPt-decorated boron-doped graphene (AuPt-BG) nanosheets as a signal amplification platform to detect cancer antigen 153 (CA153). Highly open, porous AuPt-BG films were synthesized using one-step electron-assisted hot-filament chemical vapor deposition. The Au-Pt alloy nanoparticles were dispersed on BG nanosheets to improve their biocompatibility, and antibodies (Ab) were directly bonded to the AuPt-BG electrode. The architectures enlarged the loading of CA153Ab and efficiently catalyzed the Fe(CN)63-/4- reaction, ultimately amplifying the signals. This novel strategy allows the simultaneous detection of CA153 in the oxidation and reduction channels, improving the reliability of the detection results. The AuPt-BG-based immunosensor exhibited a lower detection limit (0.0012 mU mL-1, S/N = 3) and wider linear range (0.1-4 × 104 mU mL-1) along with improved reproducibility, selectivity, and stability for the assay of CA153. Owing to the high process controllability of AuPt-BG films, a large-area electrode for in-vitro analyses and a flexible microelectrode for in-vivo analyses were prepared, which confirmed that the AuPt-BG-based sensor is an ideal CA153 detection platform for clinical diagnosis and practical applications.

Preparation of self-supporting vertically/horizontally grown graphene microelectrodes for neurotransmitter determination.

The development of microelectrodes for the rapid in situ detection of neurotransmitters and their metabolic levels in human biofluids has considerable significance in biomedical research. In this study, self-supported graphene microelectrodes with B-doped, N-doped, and B- and N-co-doped vertical graphene (BVG, NVG, and BNVG, respectively) nanosheets grown on horizontal graphene (HG) were fabricated for the first time. The high electrochemical catalytic activity of BVG/HG on monoamine compounds was explored by investigating the influence of B and N atoms and the VG layer thickness on the response current of neurotransmitters. Quantitative analysis using the BVG/HG electrode in a blood-like environment with pH 7.4 indicated that the linear concentration ranges were 1-400 and 1-350 µM for dopamine (DA) and serotonin (5-HT), with limits of detection (LODs) of 0.271 and 0.361 µM, respectively. For tryptophan (Trp), the sensor measured a wide linear concentration range of 3-1500 µM over a wide pH range of 5.0-9.0, with the LOD fluctuating between 0.58 and 1.04 µM. Furthermore, the BVG/HG microelectrodes could be developed as needle- and pen-type sensors for the detection of DA, 5-HT, and Trp in human blood and gastrointestinal secretion samples.

Molecularly imprinted Ni-polyacrylamide-based electrochemical sensor for the simultaneous detection of dopamine and adenine.

Molecularly imprinted polymer (MIP) membranes prepared in situ present several advantages: they maintain the original morphology, adhere strongly to the collector, and exhibit a controllable structure. In this study, a Ni-polyacrylamide (PAM)-MIP matrix was fabricated in situ on glassy carbon via the one-step electro-polymerization of AM monomers in the presence of Ni and template molecules. Ni2+ ions were introduced as oxidants to promote AM polymerization and bulking agents to fabricate a three-dimensional porous PAM-MIP matrix. The Ni-PAM-based MIP sensor exhibited a quantitative dual response toward dopamine (DA) and adenine (Ade) in the pH range of 5.0-9.0. The linear concentration range changed depending on the pH environment, and the concentrations of DA and Ade ranged from 0.6 to 200 µM and from 0.4 to 300 µM, respectively. The ranges of detection limits (S/N = 3) were 0.12-0.37 µM for DA and 0.15-0.36 µM for Ade. In addition, the dual-MIP sensor exhibited high reliability in the detection of DA and Ade in human serum owing to its excellent anti-interference ability and long-term stability. The technique developed in this study is expected to facilitate the construction of multi-target response electrochemical biosensors and the reliable determination of small molecules with high selectivity and stability.