A covalent-organic framework-based platform for simultaneous smartphone detection and degradation of aflatoxin B1.

This study developed a smartphone-based biosensor that could simultaneously detect and degrade aflatoxin B1 (AFB1). A donor-acceptor covalent organic framework (COF) was bound onto the surface of stainless-steel mesh (SSM) via the in-situ synthesis, which was used to immobilize the aptamer (Apt) to specifically capture AFB1 and was also as a photocatalyst to degrade AFB1. Au@Ir nanospheres were synthesized, which exhibited better peroxidase catalytic activity (Km=5.36 × 10-6 M, Vmax=3.48 × 10-7 Ms-1, Kcat=1.00 × 107 s-1) than Ir@Au nanospheres, so Au@Ir nanospheres were linked with Apt2 to be utilized as the signal probe. The density functional theory calculation also described that Au@Ir nanospheres possessed the lower energy barriers to decompose H2O2 than Ir@Au nanospheres. Coupled with the "Color Picker" application in the smartphone, the established "sandwich-structure" colorimetric method exhibited a linear range of 0.5-200 µg L-1 and a detection limit of 0.045 µg L-1. The photocatalytic capacity of SSM/COF towards AFB1 was investigated and the degradation rate researched 81.14 % within 120 min under the xenon lamp irradiation, and the degradation products were validated by ESI-MS. It was applied for the detection of AFB1 in peanuts, corn, and wheat samples. Recoveries were ranging from 77.90 % to 112.5 %, and the matrix effect was 75.10-111.6 %. Therefore, the smartphone-based biosensor provided a simple, fast, and sensitive platform for the detection of AFB1, and meanwhile could realize the efficient degradation of AFB1.

Poly (ionic liquid) cross-linked hydrogel encapsulated with AuPt nanozymes for the smartphone-based colorimetric detection of zearalenone.

A poly (ionic liquid) enhanced poly(acrylamide-acrylic acid) (PIL-PAM/AA) hydrogel-based colorimetric sensor was designed to detect zearalenone (ZEN). Different AuxPty nanoparticles were synthesized via the on-pot method. Through the kinetic analysis and the theoretical calculation, Au0.4Pt0.6 possessed the relatively low energy barriers to adsorb and decompose H2O2 so that it exhibited relatively better catalytic activity (Km = 2.02 × 10-3, Vmax = 6.14 × 10-7). AuPt nanoparticles were encapsulated into PIL-PAM/AA hydrogel via the interaction between aptamer and cDNA. In the presence of ZEN, the embedded AuPt nanoparticles were released to complete the catalytic reaction. Coupled with the smartphone application, the established method provided the linear range of 1-250 ng mL-1, with a detection limit of 0.6979 ng mL-1 for ZEN. Meanwhile, it also possessed excellent selectivity and good anti-interference performance. In wheat and corn samples, spiked recoveries were ranging from 75% to 113.30%.

Ionic liquid-enhanced silica aerogels for the specific extraction and detection of aflatoxin B1 coupled with a smartphone-based colorimetric biosensor.

The polymer ionic liquid (1-allyl-3-butylimidazolium bromide) enhanced silica aerogel was modified onto the surface of stainless-steel mesh to immobilize aptamer-1 for the specific recognition of AFB1. The porous channels of silica aerogel could prevent the interference of macromolecules in food samples. Enzyme kinetic analysis showed that the MoS2/Au was an effective peroxidase mimic with a relatively low Michaelis constant (Km) value of 0.17 mM and a high catalytic rate of 3.87 × 10-8 mol (L·s)-1, which exhibited obvious superiority compared with horseradish peroxidase. The established "sandwich-structure" biosensor was coupled with the smartphone "Color Picker" application was used to detect AFB1 with a wide linear range (1-100 ng mL-1) and low detection limit (0.25 ng mL-1). The anti-interference ability of the established biosensor was evaluated by adding different concentrations of standards in corn, peanut, and wheat and matrix effects were 90.84-106.11 %. The results showed that this method demonstrated high specificity, sensitivity, rapidity and low interference in food samples.

Ionic liquids functionalized Fe3O4-based colorimetric biosensor for rapid determination of ochratoxin A.

A stainless steel mesh (SSM) with the feature of flexibility was employed as the colorimetric biosensor substrate, and aptamer was bond onto the surface of the SSM. Through the cross-linking of ionic liquids (ILs), AuPt nanoparticles were deposited  onto the surface of Fe3O4 material to obtain a magnetic nanozyme with high peroxidase catalytic activity and rapid color change. Through the competing interaction of OTA and cDNA with aptamer, AuPt@IL@Fe3O4 signal probe was separated to catalyze the 3,3',5,5'-tetramethylbenzidine/hydrogen peroxide (TMB/H2O2) system to observe the color by bare eye and record the absorbance at 652 nm using a UV-spectrophotometer. Through the study of the catalytic properties on the basis of the Michaelis equation, AuPt@IL@Fe3O4 nanozyme presented a Vmax of 3.85 × 10-8 M s-1 and Km of 0.01 mM. Under the optimized conditions, the linear range of the colorimetric biosensor towards OTA was 5-100 ng mL-1, and the detection limit was 0.078 ng mL-1. This biosensor was applied to beer and corn samples with recoveries of 70.4-102.6% and 93.3-104.7%, respectively. Results showed that this sensor is a portable, rapid, economical, sensitive visual sensing platform towards mycotoxin in real samples.

Integration of Metallic Nanomaterials and Recognition Elements for the Specifically Monitoring of Pesticides in Electrochemical Sensing.

Although all countries have been controlling the excessive use of pesticides, incidents of pesticide residues still existed. Electrochemical biosensors are extensively applied detection techniques to monitor pesticides with the help of different types of biorecognition components mainly including, antibodies, aptamers, enzymes (i.e., acetylcholinesterase, organophosphorus hydrolase, etc.), and synthetic molecularly imprinted polymers. Besides, the electrode materials mainly affected the sensitivity of electrochemical biosensors. Metallic nanomaterials with various structures and excellent electrical conductivity were desirable choice to construct electrochemical platforms to achieve the detection with high sensitivity and good specificity toward the target. This work reviewed the developed metallic materials including monometallic nanoparticles, bimetallic nanomaterials, metal atoms, metal oxides, metal molybdates, metal-organic frameworks, MXene, etc. Integration of recognition elements endowed the electrode materials with higher specificity toward the target pesticide. Besides, future challenges of metallic nanomaterials-based electrochemical biosensors for the detection of pesticides are also discussed and described.

Electrochemical (Bio)Sensors for the Detection of Organophosphorus Pesticides Based on Nanomaterial-Modified Electrodes: A Review.

Organophosphorus pesticides were easily remained in fruits and vegetables which would be harm to the environmental safety and human health. In recent years, due to the simple preparation process, fast response and high sensitivity, the electrochemical (bio)sensors have received increasing attention, which were extensively used as the sensing platform for the detection of OPPs. The mechanisms for the determination of OPPs mainly included redox of nitrophenyl OPPs, enzyme hydrolysis and inhibition, immunosensor, aptasensor. Nowadays, the mainly explored electrode material has focused on metal-organic frameworks, metal and metal derivatives, carbon materials (carbon nanotube, graphene, g-C3N4), MXene, etc. These nanomaterials played important roles in the electrochemical (bio)sensors, which included: (a) as an electrocatalyst to promote the redox reaction, (b) as a carrier to load the enzyme or aptamer, (c) as a recognizer to identify the targets. The nanomaterials-based electrochemical (bio)sensor was a rapid, cost-effective methods to detect OPPs with high sensitivity. Besides, this review compared the analytical performance of different nanomaterials-based electrochemical (bio)sensors, and also identified the key challenges in the future. It would provide new ideas and insights to the further development and application of electrochemical (bio)sensors and the detection of pesticides in real samples.

Hydrophilic Covalent Organic Frameworks Coated Steel Sheet As a Mass Spectrometric Ionization Source for the Direct Determination of Zearalenone and Its Derivatives.

Zearalenone has attracted worldwide attention due to its toxic properties and threat to public health. A rapid determination method for zearalenone and its derivatives by hydrophilic covalent organic frameworks coated steel sheet (HCOFCS) combined with ambient mass spectrometry (AMS) was developed. The HCOFCS behaved as both a tip for solid-phase microextraction and a solid substrate for electrospray ionization mass spectrometry (ESI-MS). To evaluate the HCOFCS-ESI-MS method, five zearalenone and its derivatives in milk samples were determined, including zearalenone (ZEA), α-zearalenol (α-ZEL), ß-zearalenol (ß-ZEL), α-zearalanol (α-ZAL), and ß-zearalanol (ß-ZAL). After the extraction procedure, the HCOFCS was directly added with a high voltage for ESI-MS, and the analysis could be completed within 1 min. The developed method showed good linearity in the range 0.1-100 µg/L with a coefficient of determination (R2) > 0.9991. The limits of detection (LODs) and limits of quantitation (LOQs) ranged from 0.05 to 0.1 and 0.2 to 0.3 µg/L, respectively. The results demonstrated that the HCOFCS combined with ESI-MS can be used for the rapid and sensitive determination of trace ZEA and its derivatives in milk samples with satisfactory recoveries from 80.58% to 109.98% and reproducibility with relative standard deviations (RSDs) no more than 11.18%. Furthermore, HCOFCS showed good reusability, which could reuse at least 10 extraction cycles with satisfactory adsorption performance.

An aptamer and flower-shaped AuPtRh nanoenzyme-based colorimetric biosensor for the detection of profenofos.

In this work, a simple, sensitive and selective colorimetric method was established for the detection of profenofos. Firstly, novel flower-shaped AuPtRh trimetallic nanospheres were synthesized via a simple one-pot method, and had outstanding peroxidase catalytic activity. AuPtRh nanospheres with a great specific surface area were linked with an aptamer via Au-S and Pt-S bonds to specifically recognize profenofos. A graphene oxide grafted stainless-steel mesh (SSM-GO) was prepared to be a carrier and the aptamer-AuPtRh was nonspecifically adsorbed on the surface of SSM-GO, which was to be the capture probe for the detection of profenofos in real samples. They were characterized and confirmed by transmission electron microscopy, atomic force microscopy, etc. Through the investigation of the catalytic performance on the basis of the Michaelis equation, the Vmax of AuPtRh nanospheres was 22.27 × 10-8 M s-1, and Km was 0.6632 mM, which indicated that the affinity of AuPtRh nanospheres was relatively higher than that of horseradish peroxidase and Au NPs. In the presence of profenofos, the aptamer-AuPtRh would specifically combine with profenofos, which would further detach from SSM-GO. Then, it was introduced into the 3,3',5,5'-tetramethylbenzidine/H2O2 (TMB/H2O2) system to form blue oxTMB. The linear range of this colorimetric biosensor was 1-300 ng L-1 and the limit of detection was 0.725 ng L-1. It also had good recovery and anti-interference ability in real samples, which provided a new strategy for the rapid detection of pesticides.

Progress in Nanomaterials-Based Enzyme and Aptamer Biosensor for the Detection of Organophosphorus Pesticides.

With the improvement of people's safety awareness, the requirement of pesticide detection is gradually increasing, and many new detection methods toward Organophosphorus pesticide (OPs) has been further developed and applied. Nanomaterials-based biosensors have played an important role in the trace detection of OPs. This article mainly introduces the detection principle of enzymes and aptamers as the identification element of biosensors. Various nanomaterials (i.e., metals and metal oxides, carbon nanotubes, graphene and graphene oxide, quantum dots, metal organic frameworks, molecular imprinted polymers, etc.) possess their unique properties and play different roles in the enzyme and aptamer-based biosensors toward OPs: (a) to produce the optical or electrochemical signal; (b) as a carrier to load the enzyme or aptamer; (c) to enhance the signal response. Besides, the intelligent portable devices provide the possibility to realize the onsite and real-time detection. The limitations of some nanomaterials and the future development are discussed. Finally, the future of enzyme and aptamer-based biosensors has prospected.

[Determination of organophosphorus pesticides based on graphene oxide aerogel solid phase extraction column].

A graphene oxide aerogel was prepared and directly filled in a solid phase extraction (SPE) column without the aid of silica or other substrates. The aerogel was used to extract and detect residual organophosphorus pesticides (phoxim, temephos, fenthion, and fenitrothion) in food, and exhibited good elasticity and high mechanical strength. The graphene oxide aerogel was prepared by freeze-drying. Its morphology and physical properties were characterized by scanning electron microscopy, infrared spectroscopy, and BET surface adsorption. Results proved the successful synthesis of the graphene oxide aerogel. Scanning electron micrographs of the aerogel exhibited a layered and fold structure, with a surface area of 740.51 m2/g. The effect of experimental conditions on the extraction recovery of organophosphorus pesticides was systematically studied through a series of single-factor experiments. Due to limited adsorption sites, sample volumes of 5-60 mL were investigated, and 15 mL was determined was the optimum sample volume. The rate of sample loading was investigated in the range of 0.8-3.0 mL/min. When the rate of sample loading was higher than 3.0 mL/min, the insufficient contact between the analytes and sorbent appeared to cause a decrease in the extraction recovery. A lower rate of sample loading would prolong the operation time due to the re-elution of organophosphorus pesticides. The sample pH was optimized from a pH range of 2-11. An acidic solution was found to be good for inducing electrostatic interactions between the graphene oxide aerogel and organophosphorus pesticides. The maximum extraction recoveries were obtained at pH 4. Three eluents (acetonitrile, methanol, and acetone) were explored for optimization, and results showed that acetonitrile was the most appropriate eluent. The eluent volume (0.6-1.2 mL) was also investigated, and the optimal value was found to be 1.0 mL. Compared with commercial extraction materials including C18 silica, the anion exchange column (SAX), amino (-NH2), and Florisil, the extraction recovery of this new material showed distinct improvement. The lifetime of the extraction column directly filled with the graphene oxide aerogel was investigated. The column could be repeatedly used for 15 times, which overcame the issue of blocking of the sieve plates of fragmented graphene nanosheets dispersed without any matrix support. The linearities of the four organophosphorus pesticides were 1-200 µg/L for phoxim, temephos, and fenthion, and 2-200 µg/L for fenitrothion. The linear correlation coefficients were all ≥0.9949, and limits of detection were in the range of 0.2-0.5 µg/L. An extraction column was used to extract the analytes continuously for five times, and the RSDs of the extraction recoveries were ≤6.5%. Subsequently, five extraction columns were used to extract the analytes under the same conditions, and the RSDs of the extraction recoveries were ≤11.3%. Finally, the established method was applied for the extraction and detection of a real sample (apple peel); no organophosphorus pesticide was detected in the apple peel. The recoveries for spiked standard solutions were between 70.5% and 93.6%, and RSDs were ≤10.4%.