Rational design of molecularly imprinted electrochemical sensor based on Nb2C-MWCNTs heterostructures for highly sensitive and selective detection of Ochratoxin a.

Developing an efficient method for screening Ochratoxin A (OTA) in agriculture products is vital to ensure food safety and human health. However, the complex food matrix seriously affects the sensitivity and accuracy. To address this issue, we designed a novel molecularly imprinted polymer (MIP) electrochemical sensor based on multiwalled carbon nanotube-modified niobium carbide (Nb2C-MWCNTs) with the aid of the density functional theory (DFT). In this design, a glassy carbon electrode (GCE) was first modified by Nb2C-MWCNTs heterostructure. Afterward, the MIP layer was prepared, with ortho-toluidine as a functional monomer selected via DFT and OTA acting as a template on the surface of Nb2C-MWCNTs/GCE using in-situ electropolymerization. Electrochemical tests and physical characterization revealed that Nb2C-MWCNTs improved the sensor's active surface area and electron transmission capacity. Nb2C-MWCNTs had a good synergistic effect on MIP, endowing the sensor with high sensitivity and specific recognition of OTA in complex food matrix systems. The MIP sensor showed a wide linear range from 0.04 to 10.0 µM with a limit of detection (LOD) of 3.6 nM. Moreover, it presented good repeatability and stability for its highly antifouling effect on OTA. In real sample analysis, the recoveries, ranging from 89.77% to 103.70%, agreed well with the results obtained by HPLC methods, suggesting the sensor has good accuracy and high potential in practical applications.

Polydopamine@ZIFs with enhanced electrochemiluminescence quenching performance for mycotoxin detection.

Quench-type electrochemiluminescence (ECL) immunosensors are appealing for detecting small molecule contaminants in signal-on mode, for which efficient ECL quenchers are highly desirable. Here, the classical quencher of polydopamine (PDA) was transformed into a unique structure by introducing zeolite imidazole frameworks (ZIFs). Besides the inherent energy transfer quenching effect on ECL, the resulting PDA@ZIFs exhibits a high scavenging property against electrogenerated coreactant-radicals and inhibits the formation of excited luminophore. A quench-type ECL immunosensor for ochratoxin A (OTA) was developed using the PDA@ZIFs as a quencher and the g-C3N4 as a luminophore. The immunosensor showed a good response towards the OTA with a linear range of 10.0 fg/mL-1.0 ng/mL and a detection limit of 4.8 fg/mL. Acceptable recoveries of 85.7 to 109.2 % were achieved for the detection of OTA in spiked foods. This work offers valuable insight for improving the performance of quench-typed ECL biosensors.

Nanobody@Biomimetic mineralized MOF as a sensing immunoprobe in detection of aflatoxin B1.

Nanobody(Nb) is too small to carry more signal reporters, which often leads to low sensitivity in immunoassay. Herein, we proposed a novel immunoprobe integration of Nb and biomimetic mineralized metal-organic frameworks(MOF), in which plenty of succinylated horseradish peroxidase(sHRP) were encapsulated within a single MOF and the Nb was assembled on the biomimetic mineralized MOF. It overcomes the dilemma that the Nb is difficult to carry more signal reporters. Meanwhile, the mineralized MOF can protect the sHRP from denaturation and facilitate the transport of substrates to the active sites of sHRP. Electrosensing of aflatoxin B1(AFB1) was realized with a competitive format in which the target AFB1 and immobilized artificial antigen were competing for binding with the immunoprobe. Additionally, the detection signal was enlarged by the catalysis of this immunoprobe to 4-chloro-1-naphthol for producing precipitations, which blocked the channels of the immunoprobe and the redox probes of Fe(CN)63-/4- was difficult to reach the electrode surface through the channels. Hence, the as-prepared immunosensor exhibited good voltammetry responses towards the determined AFB1 in a linear range of 50.0 fg/mL - 20.0 ng/mL with a detection limit of 20.0 fg/mL. The specificity, stability, and reproducibility of this immunosensor were satisfactory. This work may provide an alternative idea for the application of Nb in immunoassay, and the idea may also be applicable to other bio-recognition elements for immunoassay.

Extraction of Camphor Tree Essential Oil by Steam Distillation and Supercritical CO2 Extraction.

The essential oil extracted from Cinnamomum camphora leaves is a mixture of volatile compounds, mainly terpenes, and is widely used in medicine, perfume and chemical industries. In this study, the extraction processes of essential oil from Cinnamomum camphora leaves by steam distillation and supercritical CO2 extraction were summarized and compared, and the camphor tree essential oil was detected by GC/MS. The extraction rate of essential oil extracted by steam distillation is less than 0.5%, while that of supercritical CO2 extraction is 4.63% at 25 MPa, 45 °C and 2.5 h. GC/MS identified 21 and 42 compounds, respectively. The content of alcohols in the essential oil is more than 35%, and that of terpenoids is more than 80%. The steam extraction method can extract volatile substances with a low boiling point and more esters and epoxides; The supercritical method is suitable for extracting weak polar substances with a high alcohol content. Supercritical CO2 extraction can selectively extract essential oil components and effectively prevent oxidation and the escape of heat sensitive substances.

A sensitive electrochemical immunosensing interface for label-free detection of aflatoxin B1 by attachment of nanobody to MWCNTs-COOH@black phosphorene.

A label-free electrochemical immunosensor has advantages of real-time and rapid detection, but it is weak in detection of small molecular toxins such as aflatoxin B1 (AFB1). The greatest obstacle to achieving this is that small molecules bound to a common immunosensing interface cannot interfere with electron transfer effectively and the detection signal is so weak. Therefore, a sensitive electrochemical immunosensing interface for small molecules is urgently needed. Here, we employed functionalized black phosphorene (BP) as electrode modification materials and anti-AFB1 nanobody (Nb) as a biorecognition element to construct a very sensitive immunosensing interface towards small molecular AFB1. The BP functionalized by carboxylic multi-walled carbon nanotubes (MWCNTs-COOH) via P-C bonding behaved with a satisfactory stability and good catalytic performance for the ferricyanide/ferrocyanide probe, while the small-sized Nb showed good compatibility with the functionalized BP and also had less influence on electron transfer than monoclonal antibody (mAb). Expectedly, the as-prepared immunosensing interface was very sensitive to AFB1 detection by differential pulse voltammetry (DPV) in a redox probe system. Under optimized conditions, a linear range from 1.0 pM to 5.0 nM and an ultralow detection limit of 0.27 pM were obtained. Additionally, the fabricated immunosensor exhibited satisfactory stability, specificity, and reproducibility. The strategy proposed here provides a more reliable reference for label-free sensing of small molecules in food samples.

MoS2 quantum dots and titanium carbide co-modified carbon nanotube heterostructure as electrode for highly sensitive detection of zearalenone.

A novel electrochemical sensor has been fabricated for sensitive determination of zearalenone (ZEA) in food samples based on molybdenum disulfide quantum dots (MoS2 QDs) and two-dimensional titanium carbide (2D-Ti3C2Tx MXene) co-modified multi-walled carbon nanotube (MWCNT) heterostructure. Physical and electrochemical characterizations reveal that 2D-Ti3C2Tx and MoS2 QDs co-modified MWCNTs yields synergistic signal amplification effect, together with large specific surface area and excellent conductivity for the heterostructure, endowing the developed sensor with high detection performance to ZEA. Under optimized conditions, the sensor shows a wide linear range from 3.00 to 300 ng mL-1 and a low limit of detection (LOD) of 0.32 ng mL-1, which is far lower than the maximum residue limits (MRLs) settled by the European Commission. In addition, it exhibits excellent selectivity, high reproducibility with a relative standard deviation (RSD) of 1.1%, and good repeatability (RSD 1.1%). In real sample analysis recoveries ranged from 94.8 to 105% showing the proposed electrochemical sensor has high potential in practical applications. This work presents an effective and valuable pathway for the use of novel heterostructure in the biosensing field.

Multiwalled carbon nanotubes modified two dimensional MXene with high antifouling property for sensitive detection of ochratoxin A.

Electrochemical sensor has great potential in the detection of small molecules by virtues of low cost, fast response, and easy to miniaturization. However, electrochemical sensing of ochratoxin A (OTA) was seriously hindered by the heavy electrode-fouling effect and poor electrochemical activity inherent from OTA molecular. Herein, two-dimensional titanium carbide (2D Ti3C2) MXene incorporated with carboxylic multiwalled carbon nanotubes (cMWCNTs) was developed as a glassy carbon electrode modifier for rapid and sensitive detection of OTA. Physical characterizations combined with electrochemical techniques revealed that cMWCNTs can not only prevent the restacking of 2D Ti3C2nanosheets but also facile its electron transfer, leading to a nanohybrid with a high specific surface and good electrocatalytic activity to OTA. Under optimal conditions, the electrochemical sensor showed a good linear response to OTA in a concentration range from 0.09 to 10µmol·l-1and a low detection limit (LOD) of 0.028µmol·l-1. The proposed sensor was impelled successive times to detect OTA, a good repeatability was obtained, indicating the constructed sensor possessed good anti-fouling property. Moreover, satisfactory recoveries between 91.8% and 103.2% were obtained in the real sample analysis of grape and beer, showing that the developed sensing technique is reliable for the screening of trace OTA in food resources.

Anchoring Metallic MoS2 Quantum Dots over MWCNTs for Highly Sensitive Detection of Postharvest Fungicide in Traditional Chinese Medicines.

Carbendazim, a very common contamination to the traditional Chinese medicines (TCMs), has posed serious threat to the environment and human health. However, sensitive and selective detection of carbendazim (MBC) in the TCMs is a big challenge for their complex chemical constituents. In this work, a 0D/1D nanohybrid was developed by anchoring 1T-phased MoS2 quantum dots (QDs) over multiwall carbon nanotubes (MWCNTs) via a facile assembly method. High-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis (TGA) together with EIS reveal that the 1T-phased QDs can anchor over MWCNTs via van der Waals forces, and the anchoring improves the nanohybrid surface area and conductivity. Therefore, the electrochemical sensor fabricated based on the MoS2 QDs@MWCNT nanohybrid shows excellent catalytic activity to MBC oxidation. Under optimized conditions, the sensor presents a linear voltammetry response to MBC concentration from 0.04 to 1.00 µmol·L-1, a low detection limit of 2.6 × 10-8 mol·L-1, as well as high selectivity, good reproducibility, and long-term stability. Moreover, the sensor has been successfully employed to determine MBC in two typical TCMs and the obtained recoveries are in good accordance with the results achieved by HPLC, showing that the constructed sensor plate holds great practical application in MBC analysis with complex matrix.

Phosphorene nanocomposite with high environmental stability and antifouling capability for simultaneous sensing of clenbuterol and ractopamine.

A series of phosphorene (BP) nanocomposites was prepared to realize simultaneous electrochemical determination of clenbuterol (CLB) and ractopamine (RAC). CLB and RAC are the most commonly used ß-agonists in animal-derived food. The BP nanohybrid was obtained by co-decoration with both mono(6-mercapto-6-deoxy)-ß-cyclodextrin and poly(3,4-ethylenedioxythiophene) nanoparticles. It displays high stability, antifouling capability, a large electrochemical active surface and good electrochemical response. The electrochemical assisted antifouling strategy was selected by further eliminating the fouling of the electrode surface using continuous cyclic voltammetry. The electrode was employed for electrochemical sensing of CLB and RAC at typical peak voltages of 0.8 and 1.0 V (vs. SCE). Responses are linear in the 0.3-90 µM concentration range for CLB, and from 0.3 to 9.4 µM for RAC under optimal conditions. The limit of detection are 0.14 and 0.12 µM, respectively. The sensor was employed for simultaneous determination of CLB and RAC in (spiked) beef, feed and bovine serum samples with acceptable recoveries. Graphical abstractAn electrochemically assisted anti-fouling method for simultaneous voltammetric nanosensing of clenbuterol (CLB) and ractopamine (RAC) in edible cattle product samples using high-stable and anti-foul phosphorene (BP) co-decorated with mono(6-mercapto-6-deoxy)-ß-cyclodextrin (S-ß-CD) and poly(3,4-ethylenedioxythiophene) (PEDOTNPs).