Recent advances of nanomaterial-based optical sensor for the detection of benzimidazole fungicides in food: a review.

The abuse of pesticides in agricultural land during pre- and post-harvest causes an increase of residue in agricultural products and pollution in the environment, which ultimately affects human health. Hence, it is crucially important to develop an effective detection method to quantify the trace amount of residue in food and water. However, with the rapid development of nanotechnology and considering the exclusive properties of nanomaterials, optical, and their integrated system have gained exclusive interest for accurately sensing of pesticides in food and agricultural samples to ensure food safety thanks to their unique benefit of high sensitivity, low detection limit, good selectivity and so on and making them a trending hotspot. This review focuses on recent progress in the past five years on nanomaterial-based optical, such as colorimetric, fluorescence, surface-enhanced Raman scattering (SERS), and their integrated system for the monitoring of benzimidazole fungicide (including, carbendazim, thiabendazole, and thiophanate-methyl) residue in food and water samples. This review firstly provides a brief introduction to mentioned techniques, detection mechanism, applied nanomaterials, label-free detection, target-specific detection, etc. then their specific application. Finally, challenges and perspectives in the respective field are discussed.

Lanthanide ion (Ln3+ )-based upconversion sensor for quantification of food contaminants: A review.

The food safety issue has gradually become the focus of attention in modern society. The presence of food contaminants poses a threat to human health and there are a number of interesting researches on the detection of food contaminants. Upconversion nanoparticles (UCNPs) are superior to other fluorescence materials, considering the benefits of large anti-Stokes shifts, high chemical stability, non-autofluorescence, good light penetration ability, and low toxicity. These properties render UCNPs promising candidates as luminescent labels in biodetection, which provides opportunities as a sensitive, accurate, and rapid detection method. This paper intended to review the research progress of food contaminants detection by UCNPs-based sensors. We have proposed the key criteria for UCNPs in the detection of food contaminants. Additionally, it highlighted the construction process of the UCNPs-based sensors, which includes the synthesis and modification of UCNPs, selection of the recognition elements, and consideration of the detection principle. Moreover, six kinds of food contaminants detected by UCNPs technology in the past 5 years have been summarized and discussed fairly. Last but not least, it is outlined that UCNPs have great potential to be applied in food safety detection and threw new insight into the challenges ahead.

A dual-mode fluorescence and colorimetric sensing platform for efficient detection of ofloxacin in aquatic products using iron alkoxide nanozyme.

Trace detection of ofloxacin (OFL) with high sensitivity, reliability, and visual clarity is challenging. To address this, a novel dual-modal aptasensor with fluorescence-colorimetric capabilities was designed that exploit the target-induced release of 3,3',5,5'-tetramethylbenzidine (TMB) molecules from aptamer-gated mesoporous silica nanoparticles (MSNs), the oxidase-like activity of iron alkoxide (IA) nanozyme, and the fluorescence attributes of core-shell upconversion nanoparticles. Therefore, the study reports a dual mode detection, with a fluorescence detection range for OFL spanning from 0.1 µg/kg to 1000 µg/kg (and a detection limit of 0.048 µg/kg). Additionally, the colorimetric method offered a linear detection range of 0.3 µg/kg to 1000 µg/kg, with a detection limit of 0.165 µg/kg. The proposed biosensor had been successfully applied to the determination of OFL content in real samples with satisfactory recoveries (78.24-96.14 %).

Enhanced detection of acrylamide using a versatile solid-state upconversion sensor through spectral and visual analysis.

Acrylamide (AM) generally forms in high-temperature processes and has been classified as a potential carcinogen. In this study, we put forward a maneuverable solid-state luminescence sensor using polydimethylsiloxane (PDMS) as the matrix coupled with upconversion nanoparticles as the indicator. The core-shell upconversion nanoparticles emitting cyan light were uniformly encapsulated in PDMS. Then it was further modified with complementary DNA of AM aptamer. The nanocrystalline fluorescein isothiocyanate isomer (FITC), coupled with AM aptamer, was attached to the surface of PDMS. FITC effectively quenched the upconversion luminescence through fluorescence resonance energy transfer (FRET). The introduction of AM resulted in preferentially bound to aptamer caused the separation of the quencher and the donor, and led to luminescence recovery. The developed sensor was applied for both spectral and visual monitoring, demonstrating a detection limit (LOD) of 1.00 nM and 1.07 nM, respectively. Importantly, in the actual foodstuffs detection, there is no obvious difference between the results of this study and the standard method, which indicates the developed method has good accuracy. Therefore, this solid-state sensor has the potential for on-site detection using a smartphone device and an Android application.

Bipyridine-mediated fluorescence charge transfer process based on copper ion grafted upconversion nanoparticle platform for ciprofloxacin sensing in aquatic products.

In this work, an ultrasensitive ciprofloxacin (CIP) detection strategy has been established based on copper (Cu2+) ions-induced strong charge transfer in poly acrylic acid (PAA) functionalized upconversion nanoparticles (UCNPs)/2,2-bipyridine (bipy) system. The positively charged Cu2+ ions electrostatically adhere to the surface of the PAA-UCNPs and deactivate the fluorescence via a charge transfer process. The bipy in this hybrid system controls the aggregation by chelating in proximity to the Cu2+ center. Due to the strong affinity between pyridone oxygen and carboxy oxygen, CIP coordinates in high stoichiometry with the bipy-Cu complex as compared to the PAA-UCNPs, causing the trapped fluorescence to be released in an amount equivalent to the target concentration. Under the optimum assay conditions, a good calibration plot (0.05-1000 ng/mL) was acquired with a detection limit of 0.13 ng/mL. The satisfactory recoveries (85.93-96.87%) for real prawn and fish samples were further validated by enzyme-linked immunoassays (P > 0.05).

Label-free detection of trace level zearalenone in corn oil by surface-enhanced Raman spectroscopy (SERS) coupled with deep learning models.

Surface-enhanced Raman spectroscopy (SERS) and deep learning models were adopted for detecting zearalenone (ZEN) in corn oil. First, gold nanorods were synthesized as a SERS substrate. Second, the collected SERS spectra were augmented to improve the generalization ability of regression models. Third, five regression models, including partial least squares regression (PLSR), random forest regression (RFR), Gaussian progress regression (GPR), one-dimensional convolutional neural networks (1D CNN), and two-dimensional convolutional neural networks (2D CNN), were developed. The results showed that 1D CNN and 2D CNN models possessed the best prediction performance, i.e., determination of prediction set (RP2) = 0.9863 and 0.9872, root mean squared error of prediction set (RMSEP) = 0.2267 and 0.2341, ratio of performance to deviation (RPD) = 6.548 and 6.827, limit of detection (LOD) = 6.81 × 10-4 and 7.24 × 10-4 µg/mL. Therefore, the proposed method offers an ultrasensitive and effective strategy for detecting ZEN in corn oil.

A solid-phase capture probe based on upconvertion nanoparticles and inner filter effect for the determination of ampicillin in food.

Ampicillin (AMP) is commonly used to treat diseases caused by bacterial infections as a veterinary drug. However, the abuse of AMP can lead to residues in food and ultimately cause harm to humans. Thus, it is significant to construct a reliable system for AMP detection. Here, we developed an inner filter effect system based on a solid-phase capture probe and the catalysis of platinum nanoparticles (PtNPs) for AMP determination in food. In the presence of AMP, PDMS captured AMP then combined with aptamer-functionalized PtNPs, which catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine, resulting in upconversion fluorescence quenching. The results showed the fluorescence intensity of upconversion nanoparticles was related to AMP concentration (0.5-100 ng·mL-1) with an LOD of 0.32 ng·mL-1, which made quantification of AMP possible. The method also achieved a satisfactory recovery rate (96.89-112.92%) and can be used for AMP detection in food samples with selectivity and sensitivity.

An upconversion nanosensor for rapid and sensitive detection of tetracycline in food based on magnetic-field-assisted separation.

Tetracycline, a broad-spectrum antibiotic, has been widely used in disease treatment and other fields. However, due to the unreasonable use, its residue remains in food which eventually harms human health. Here described an upconversion nanosensor for tetracycline detection based on magnetic separation and electrostatic adsorption. To identify tetracycline, tetracycline aptamer, and europium ions (Eu3+) were introduced in the system. According to the electrostatic adsorption principle, Eu3+ exposed core-shell UCNPs were bound to negative complex of magnetic nanoparticles (MNPs) and aptamer. In the presence of tetracycline, UCNPs separated with MNPs-aptamer and remained in the supernatant by an external magnetic field. Under optimal conditions, the linear detection range of tetracycline was 0.5-1000 ng·mL-1, and the detection limit was 0.17 ng·mL-1. It has been successfully applied to detect tetracycline in food samples. The constructed method provided broad prospects for tetracycline detection with the merits of simple operation, high sensitivity, excellent repeatability, and selectivity.

A turn-on fluorescence sensor for rapid sensing of ATP based on luminescence resonance energy transfer between upconversion nanoparticles and Cy3 in vivo or vitro.

Adenosine triphosphate (ATP) is an energy molecule of significant importance, and, the monitoring of ATP in living cells is considerable for the clinical diagnosis of many related diseases, including cancer. Upconversion nanoparticles (UCNPs) have recently been attracting widespread interest in biomedical applications due to their chemical and thermal stability, high sensitivity, good biocompatibility, and excellent tissue penetration. Herein, a Cy3-aptamer-cDNA- UCNPs nanosensor was synthesized, based on the luminescence resonance energy transfer (LRET) between UCNPs and Cy3 for monitoring ATP in living cells. It showed a selective sensing ability for ATP levels by changes of fluorescence intensity of UNCPs at 536 nm. The investigated biosensor showed a precise, efficient detection with sufficient selectivity which was achieved through the optimization of conditions. In the range of 1-1000 µM, the ATP-induced changes of the fluorescence intensity were linearly proportional to the ATP concentrations. Furthermore, the cytotoxicity assay revealed that the UCNPs sensor exhibited favorable biocompatibility, implicating the use of UCNPs in vivo imaging. This study highlights the potential of using a combination of UCNPs and ATP-binding aptamer to design an ATP-activatable probe for fluorescence-mediated imaging in living cells. These results implied that the nanosensor can be applicable for the monitoring of intracellular ATP by fluorescence imaging and the quantitative analysis of biological liquids.

An upconversion biosensor based on DNA hybridization and DNA-templated silver nanoclusters for the determination of acrylamide.

Acrylamide is widely present in many fried and baked foods, that has been proved as potentially carcinogenic to humans. In this work, a novel biosensor using core-shell upconversion nanoparticles (CSUCNPs) with aptamer as recognized element was designed for the determination of acrylamide. The principle of this work was based on the fluorescence resonance energy transfer (FRET) process from CSUCNPs to silver nanoclusters (AgNCs). Whereas the binding between acrylamide and the aptamer disturbed the DNA structure and inhibited the synthesis of AgNCs, which induced a higher fluorescence intensity. Under the optimal conditions, a low limit of detection (LOD) was calculated as 1.13 nM in the range of 1-105 nM. This biosensor was further applied in the spiked food samples to validate the applicability that recoveries were at the range of 78.52-117.09% with a relative standard deviation of 1.54-10.46%. The approach was compared with the standard HPLC method in great agreement (P ＞ 0.05).

A turn-on upconversion fluorescence sensor for acrylamide in potato chips based on fluorescence resonance energy transfer and thiol-ene Michael addition.

This study describes a turn-on upconversion fluorescence sensor for the detection of acrylamide (AA) based on glutathione (GSH) modulated turn-on fluorescence strategy. Polyethyleneimine-modified upconversion nanoparticles were first prepared by the hydrothermal method and then Rhodamine B derivative (RBD) was loaded on their surface through non-covalent bonding. The GSH coupled with RBD and strongly quenched the upconversion fluorescence via fluorescence resonance energy transfer. Upon addition of tris (2-carboxyethyl) phosphine, the thiol-ene Michael addition reaction between GSH and AA was efficiently catalyzed, resulted in the quenched fluorescence triggered on. Under the optimum conditions, a linear detection range from 0.1 to 104 µM was implemented for AA with a limit of detection of 0.68 nM and great sensitivity was observed. Importantly, the proposed sensor was evaluated for spiked potato chips samples with a satisfactory result in contrast to high-performance liquid chromatography, confirmed its applicability for the rapid detection of AA.

A highly sensitive detection of carbendazim pesticide in food based on the upconversion-MnO2 luminescent resonance energy transfer biosensor.

Carbendazim (CBZ) pesticide residues in food products have become a growing concern in recent years. Herein, a sensitive biosensor for detecting CBZ was developed based on luminescent resonance energy transfer (LRET) from aptamer labeled upconversion nanoparticles (UCNPs, donor) to manganese dioxide (MnO2, acceptor) nanosheets. The strong overlap between the absorption spectrum of MnO2 and the UCNPs fluorescence emission allowed the luminescence quenching. With the addition of CBZ, it tended to bind with specific aptamers, which culminated in the UCNPs-aptamer dropping off MnO2 nanosheets and restoring the fluorescence. A linear calibration plot between logarithmic CBZ concentration and fluorescence intensity was acquired in the range of 0.1-5000 ng·mL-1, with a limit of detection 0.05 ng·mL-1, indicating that the UCNPs- MnO2 aptasensor is a rapid, sensitive and specific quantitative detection platform for CBZ. Furthermore, the precision and accuracy of the developed LRET biosensor was validated by HPLC method with no significant differences.

Rapid detection of mercury in food via rhodamine 6G signal using surface-enhanced Raman scattering coupled multivariate calibration.

Considering food safety and limitations of biorecognition elements, this study focused on the development of a novel method for predicting mercury (Hg2+) in fish and water samples using surface-enhanced Raman scattering (SERS) coupled wavenumber selection chemometric method. Herein, core-shell Au@Ag nanoparticles (Au@Ag NPs) were synthesized as SERS substrate, and rhodamine 6G (R6G) was used as signaling probe for Hg2+. In the presence of Hg2+, citrate ion of Au@Ag NPs induced complexation and become amalgam causes desorption of R6G occurred, resulted in decreased SERS signal intensity. Compared to surface Plasmon resonance method, SERS coupled genetic algorithm-partial least squares realized good correlation coefficient (0.9745 and 0.9773) in their prediction over the concentration ranges 1.0 × 102 to 1.0 × 10-3 µg/g. The recovery (88.45 - 94.73%) and precision (coefficient of variations, 3.28 - 5.76%) exhibiting satisfactory results suggested that the proposed method could be employed to predict Hg2+ in fish and water samples towards quality and safety monitoring.

Rapid and sensitive detection of diazinon in food based on the FRET between rare-earth doped upconversion nanoparticles and graphene oxide.

Diazinon is a typical phosphorothionate, which is widely used to prevent and control harmful organisms that endanger the agriculture productions. However, it is among the most toxic substances and can cause damage to the environment, food and human health even in very low concentrations. Hence, ultra-sensitive screening methods are urgently required for the detection of this extensively used pesticide. In this study, a rapid and sensitive fluorescence resonance energy transfer (FRET) method was developed for low concentration detection of diazinon in food. The aptamer-modified upconversion nanoparticles (Apt-UCNPs) were synthesized and conjugated with graphene oxide (GO) through π-π interaction. Due to the FRET between UCNPs and GO, the fluorescence was quenched. When diazinon was added, the aptamer preferentially bound with it, caused the separation of GO, and resulted in the enhancement of fluorescent signal. Under the optimal conditions, a wide linear detection range from 0.05 to 500 ng/mL was achieved, with a limit of detection (LOD) of 0.023 ng/mL. The proposed method was successfully applied to measure diazinon in real samples. Results showed that the proposed nanosensor offers an efficient, specific and simple approach for the detection of diazinon in food and has a high potential for food safety and quality control.

[Study of target pegylated recombinant mutant human granulocyte colony stimulating factor].

Recombinant mutant human granulocyte colony stimulating factor (rmhG-CSF) was pegylated, purified and characterized. rhG-CSF was mutated in position 1,3,4,5,17, and cysteine was added in C-terminal. rmhG-CSF was pegylated by PEG-Mal 20000 and separated by ion-exchange chromatography, gel filtration chromatography. Analysis of SDS-PAGE showed thar the purity of the separated PEG-rmhG-CSF was greater than 95%. and in intro and in vivo bioactivity study showed that target modified PEG-rmhG-CSF kept full bioactivity which was better than traditional pegylation method, and longer half-life was proved in mice.