Capability of phytoremediation of glyphosate in environment by Vulpia myuros.

Glyphosate is an herbicide extensively used worldwide that can remain in the soil. Phytoremediation to decontaminate polluted water or soil requires a plant that can accumulate the target compound. Vulpia myuros is an annual fescue that can be used as a heavy mental phytoremediation strategy. Recently, it has been used to intercrop with tea plant to prohibit the germination and growth of other weeds in tea garden. In order to know whether it can be used an decontaminating glyphosate' plant in water or soil, in this study, glyphosate degradation behavior was investigated in Vulpia myuros cultivated in a hydroponic system. The results showed that the concentration of glyphosate in the nutrient solution decreased from 43.09 µg mL-1 to 0.45 µg mL-1 in 30 days and that 99% of the glyphosate molecules were absorbed by V. myuros. The contents of glyphosate in the roots reached the maximum (224.33 mg kg-1) on day 1 and then decreased. After 3 days, the content of glyphosate in the leaves reached the highest value (215.64 mg kg-1), while it decreased to 156.26 mg kg-1 in the roots. The dissipation dynamics of glyphosate in the whole hydroponic system fits the first-order kinetic model C = 455.76e-0.21 t, with a half-life of 5.08 days. Over 30 days, 80% of the glyphosate was degraded. The contents of the glyphosate metabolite amino methyl phosphoric acid (AMPA), ranged from 0.103 mg kg-1 on day 1-0.098 mg kg-1 on day 30, not changing significantly over time. The Croot/solution, Cleaf/solution and Cleaf/root were used to express the absorption, transfer, and distribution of glyphosate in V. myuros. These results indicated that glyphosate entered into the root system through free diffusion, which was influenced by both the log Kow and the concentration of glyphosate in the nutrient solution, and that glyphosate was either easily transferred to the leaves through the transpiration stream, accumulated, or degraded. The degradation of glyphosate in V. myuros indicated that it has potential as a remediating plant for environmental restoration.

Selenium foliar application contributes to decrease ratio of water-soluble fluoride and improve physio-biochemical components in tea leaves.

The tea plant accumulates elevated levels of fluoride (F) from environmental sources. Drinking tea containing high F levels poses a potential threat to human health. Selenium (Se) was applied by foliar spray to investigate its effects on F accumulation and physiology in tea plant. Foliar application of different forms of Se, i.e., Na2SeO3, Kappa-selenocarrageenan, Selenomethionine and Nanoselenium, reduced F content in tea leaves by 10.17 %-44.28 %, 16.12 %-35.41 %, 22.19 %-45.99 % and 22.24 %-43.82 %, respectively. Foliar spraying Se could increase F accumulation in pectin through increasing pectin content and pectin demethylesterification to bind more F in the cell wall, which decreased the proportion of water-soluble fluoride in tea leaves. Application of Se significantly decreased the contents of chromium (39.6 %-72.0 %), cadmium (48.3 %-84.4 %), lead (2.2 %-44.4 %) and copper (14.1 %-44.6 %) in tea leaves. Foliar spraying various forms of Se dramatically increased the Se content and was efficiently transformed into organic Se accounting for more than 80 % in tea leaves. All Se compounds increased peroxidase activity by 3.3 %-35.5 % and catalase activity by 2.6 %-99.4 %, reduced malondialdehyde content by 5.6 %-37.1 %, and increased the contents of chlorophyll by 0.65 %-31.8 %, carotenoids by 0.24 %-27.1 %, total catechins by 1.6 %-21.0 %, EGCG by 4.4 %-17.6 % and caffeine by 9.1 %-28.6 %. These results indicated that Se application could be served as a potential efficient and safe strategy diminishing the concentration of F in tea leaves.

Multi-analyte High-Throughput Microplate-SERS Reader with Controllable Liquid Interfacial Arrays.

High-throughput surface-enhanced Raman scattering (SERS) reader, especially for liquid sample testing, is of great significance and huge demand in biology, environment, and other analytical fields. Inspired by the principle of microplate reader, herein, we developed a microplate-SERS reader for semiautomatic and high-throughput assays by virtue of three-dimensional liquid interfacial arrays (LIAs). For the first time, the formation of LIA in oil-in-water state, water-in-oil state, and two-dimensional plane state is realized by operating the hydrophilicity (contact angle) of the container. Through the force analysis of LIA, the effect of organic (O) phase density on the relative position of LIA was quantified. In addition, the optimized reader offers fast and continuous semiautomatic detection of 12 samples below 10 min with great signal reproducibility (calibration with the characteristic peak of O phase as the internal standard). The isolated wells in the microplate prevent analyte cross talk, allowing accurate quantification of each sample. Multiplex analysis capability highlights that this reader has the ability of rapid identification and quantification of samples containing various analytes and concentrations. The results demonstrate high-resolution dual and triple analyte detection with fully preserved signal and Raman features of individual analytes in a mixture, which implies that it also has excellent anticounterfeiting applications. This microplate-SERS reader combines the superior advantages of the LIA, microplate, and SERS techniques to retrieve the molecular vibrational fingerprints of various chemicals in complex media.

Rapid identification of the geographic origin of Taiping Houkui green tea using near-infrared spectroscopy combined with a variable selection method.

BACKGROUND: Most studies focus on the geographically larger production areas in tea traceability. However, famous high-quality tea is often produced in a narrow range of origins, which makes traceability a challenge. In this study, Taiping Houkui (TPHK) green tea of narrow geographical origin was rapidly identified using Fourier-transform near-infrared (FT-NIR) spectroscopy. RESULTS: First, spectral information of 114 TPHK samples from four production areas was acquired. Second, the synthetic minority over-sampling technique (SMOTE) was used to balance the sample data set, and three different spectral pre-processing methods were compared. Third, three feature variable selection algorithms were used to obtain the pre-processed spectral features. Finally, extreme learning machine (ELM) models based on the variables obtained from the selected features were established to trace the TPHK origin. The optimized ELM model achieves 95.35% classification accuracy in the test set. CONCLUSION: The present study demonstrates that the optimized variable selection method in combination with NIR spectroscopy represents a suitable strategy for tea traceability in narrow regions. © 2022 Society of Chemical Industry.

Delivery of acetamiprid to tea leaves enabled by porous silica nanoparticles: efficiency, distribution and metabolism of acetamiprid in tea plants.

BACKGROUND: Pesticide residue and its poor utilization remains problematic in agricultural development. To address the issue, a nano-pesticide has been developed by incorporating pesticide acetamiprid in porous silica nanoparticles. RESULTS: This nano-pesticide had an acetamiprid loading content of 354.01 mg g-1. Testing LC50 value against tea aphids of the commercial preparation was three times that of the nano-pesticide. In tea seedlings (Camellia sinensis L.), acetamiprid was transported upward from the stem to the young leaves. On day 30, the average retained concentrations in tea leaves treated with the commercial preparation were about 1.3 times of that in the nano-pesticide preparation. The residual concentrations of dimethyl-acetamiprid in leaves for plants treated with the commercial preparation were about 1.1 times of that in the nano-pesticide preparation. Untargeted metabolomics of by LC-MS on the young leaves of tea seedlings under nano-pesticide and commercial pesticide treatments showed significant numbers of differentially expressed metabolites (P < 0.05 and VIP > 1). Between the nano-pesticide treatment group and the commercial preparation treatment group there were 196 differentially expressed metabolites 2 h after treatment, 200 (7th day), 207 (21st day), and 201 (30th day) in negative ion mode, and 294 (2nd h), 356 (7th day), and 286 (30th day) in positive ion mode. Preliminary identification showed that the major differentially expressed metabolites were glutamic acid, salicylic acid, p-coumaric acid, ribonic acid, glutamine, naringenin diglucoside, sanguiin H4, PG (34:2) and epiafzelechin. CONCLUSIONS: This work demonstrated that our nano-pesticide outperformed the conventional pesticide acetamiprid in terms of insecticidal activity and pesticide residue, and the absorption, transportation and metabolism of nano-pesticide in tea plant were different, which pave a new pathway for pest control in agricultural sector.

Fluoride absorption, transportation and tolerance mechanism in Camellia sinensis, and its bioavailability and health risk assessment: a systematic review.

Tea is the one of the most popular non-alcoholic caffeinated beverages in the world. Tea is produced from the tea plant (Camellia sinensis (L.) O. Kuntze), which is known to accumulate fluoride. This article systematically analyzes the literature concerning fluoride absorption, transportation and fluoride tolerance mechanisms in tea plants. Fluoride bioavailability and exposure levels in tea infusions are also reviewed. The circulation of fluoride within the tea plantation ecosystems is in a positive equilibrium, with greater amounts of fluoride introduced to tea orchards than removed. Water extractable fluoride and magnesium chloride (MgCl2 ) extractable fluoride in plantation soil are the main sources of absorption by tea plant root via active trans-membrane transport and anion channels. Most fluoride is readily transported through the xylem as F- /F-Al complexes to leaf cell walls and vacuole. The findings indicate that tea plants employ cell wall accumulation, vacuole compartmentalization, and F-Al complexes to co-detoxify fluoride and aluminum, a possible tolerance mechanism through which tea tolerates higher levels of fluoride than most plants. Furthermore, dietary and endogenous factors influence fluoride bioavailability and should be considered when exposure levels of fluoride in commercially available dried tea leaves are interpreted. The relevant current challenges and future perspectives are also discussed. © 2020 Society of Chemical Industry.

Cytotoxicity of 2,2',3,5',6-Pentachlorobiphenyl (PCB95) and its metabolites in the chicken embryo liver cells of laying hens.

2,2',3,5',6-Pentachlorobiphenyl (PCB95) is known as a persistent pollutant that was found in eggs in China. PCB 95 can be metabolized into OH-PCB95 and MeO-PCB95 in liver microsomes. However, the toxicity and its mechanism of PCB95 or its metabolites have been little studied on laying hens. Herein, chicken embryo liver cells of laying hens were selected and treated with different levels of PCB95 and its two metabolites, and the EC50 of PCB95, OH-PCB95, MeO-PCB95 was 80.85, 4.81 and 107.04 µg/mL respectively, indicating that OH-PCB95 is much more cytotoxic than PCB95 or MeO-PCB95. Targeted metabolomics was further used to study the effects of the parent compound and its metabolites on cell metabolism. The results showed that four primary types of glycerophospholipids were down-regulated after exposure to PCB95 and its metabolites, especially PE and PS (60% more than the control for PCB95, 40% for OH-PCB95, and less than 40% for MeO-PCB95). KEGG pathway analysis based on amino acid metabolism showed that PCB95 may mainly interfere with the amino acids involved in immune regulation (phenylalanine and tyrosine), and OH-PCB95 may be associated with genetic disoders (cysteine, methionine and purine metabolism). However, the metabolic pathways induced by MeO-PCB95 are quite different from those induced by PCB95 and OH-PCB95, affecting mainly D-glutamine and D-glutamate metabolism, alanine and glutamate metabolism, and arginine and proline metabolism; these pathways mainly regulate the elimination of excess purines and are involved in the synthesis of the amino acids required by cells. These results showed that OH-PCB95 has the highest toxicity on chicken embryo liver cells and MeO-PCB95 could be a detoxification product of PCB95 and OH-PCB95. This study contributes to the understanding of the different effects of PCB95 and its metabolites on cellular metabolism, and the data are helpful in evaluating the hepatotoxic effects of these compounds.

Washing fresh tea leaves before picking decreases pesticide residues in tea.

BACKGROUND: The use of pesticides during tea plant cultivation helps agricultural production and prevents and controls pests, diseases and weeds. It is of the utmost importance to balance pesticide application with tea quality, safety and consumer health. The uptake of pesticides into plants may lead to the presence of residues that are hazardous to human health, especially for some foliar-applied insecticides. The movability or penetration behavior of a pesticide remains unknown after it has been sprayed on a tea leaf. RESULTS: Two organophosphate (acephate, trichlorfon) and three neonicotinoid pesticides (imidacloprid, thiamethoxam and acetamiprid) were confirmed with respect to their removal from the treated fresh leaves of tea saplings via washing in a phytotron. Four of the targets have little penetrative ability into tea leaves, mainly existing (> 92%) on the tea leaf surface, except for trichlorfon (> 70%), for 30 days. With higher vapor pressures, trichlorfon and acetamiprid had relatively higher penetration ratios of 8.63-29.60% and 0.28-8.03% respectively. Two organophosphate insecticides were found to degrade more quickly, with lower final amounts of residues on and in the whole leaf compared to the neonicotinoid pesticides. In a field test, these residues could be reduced by 45-72% after a pre-harvest interval of 3 days, and by 16-89% after 7 days, when the fresh tea shoots were sprayed with 2 or 4 L m-2 water. CONCLUSION: Pesticides with different structures have different penetration abilities on the tea leaf surface, and some pesticides in commercial tea can be reduced by spraying with water before fresh leaves are picked. © 2020 Society of Chemical Industry.

Evaluation of the feasibility of short-term electrodialysis for separating naturally occurring fluoride from instant brick tea infusion.

BACKGROUND: Removing excessive naturally occurring fluoride from tea and/or infusions is difficult because the process has low efficiency and causes secondary pollution. In this study, a novel electrodialysis (ED) technology was developed. We examined the effect of crucial parameters (electrolyte concentration, operation voltage, ED duration and initial concentration of the tea infusion) on defluoridation performance using a highly efficient ion-exchange membrane with five-compartment cells. RESULTS: The most effective ED system results were obtained at an electrolyte concentration of 10 g kg-1 and operating voltage of 20 V. Moreover, the fluoride removal capacity (10.70-66.93%) was highly dependent on the ED duration (1-15 min) and initial concentration of the tea infusion (0.5-10 g kg-1 ). The longer the ED duration and the lower the initial concentration, the higher was the defluoridation performance. During ED, limited loss of the main inclusions (total polyphenols, catechins, caffeine and selected ions) was observed. Furthermore, the D201 anion resin-filled ED stack (0.5-5 g) and improvement of concentrate compartment electrolyte (≥5 times the dilute compartment electrolyte) in the ED system enhanced the defluoridation rate significantly. CONCLUSION: ED is a potentially effective method that can be used for defluoridation in the deep processing of tea products. © 2019 Society of Chemical Industry.

Real-Time Monitoring of Pesticide Translocation in Tomato Plants by Surface-Enhanced Raman Spectroscopy.

Understanding the behavior of pesticide translocation is significant for effectively applying pesticides and reducing pesticide exposures from treated plants. Herein, we applied surface enhanced Raman spectroscopy (SERS) for real-time monitoring of pesticide translocation in tomato plant tissues, including leaves and flowers, following root exposure in hydroponic and soil systems. Various concentrations of the systemic pesticide, thiabendazole, was introduced into hydroponic systems used for growing tomato plants. At selected time intervals, tomato leaves and flowers were picked and thiabendazole was measured directly under a Raman microscope after pipetting gold nanoparticle-containing solution onto the plant tissue. We found that the pesticide signals first appeared along the midrib in the lowest leaves and moved distally to the edge of the leaves. As the concentration of pesticide applied to the root was increased, the time necessary to detect the signal was decreased. The SERS surface mapping method was also able to detect thiabendazole in the trichomes of the leaves. In addition, we found a unique SERS peak at 737 cm-1 on both leaves and flowers at 4 and 6 days following the application of 200 mg/L thiabendazole to the hydroponic system. This peak appears to be coming from adenine-containing materials and may be related to the plant's response to pesticide toxicity, which could be used as a potential marker for monitoring plant responses to stresses. These results demonstrate a successful application of SERS as a rapid and effective way to study the real-time translocation behavior of pesticides in a plant system.

Insecticidal Activity and Insecticidal Mechanism of Total Saponins from Camellia oleifera.

Chemical pesticides are commonly used during the cultivation of agricultural products to control pests and diseases. Excessive use of traditional pesticides can cause environmental and human health risks. There are ongoing searches for new plant-derived pesticides to reduce the use of chemical pesticides. In this study, tea saponin extracts of different purities were extracted from Camellia oleifera seeds using AB-8 macroporous resin and gradient elution with ethanol. The insecticidal effects of the tea saponin extracts were evaluated by contact toxicity tests and stomach toxicity tests using the lepidopteran pest of tea plantation, Ectropis obliqua. The total saponins extracted using 70% ethanol showed strong contact toxicity (LC50 = 8.459 mg/L) and stomach toxicity (LC50 = 22.395 mg/L). In-depth mechanistic studies demonstrated that tea saponins can disrupt the waxy layer of the epidermis, causing serious loss of water, and can penetrate the inside of the intestine of E. obliqua. After consumption of the tea saponins, the intestinal villi were shortened and the cavities of the intestinal wall were disrupted, which resulted in larval death. This study highlights the potential of tea saponins as a natural, plant-derived pesticide for the management of plant pests.

Using stable isotope signatures to delineate the geographic point-of-origin of Keemun black tea.

BACKGROUND: Confirmation of food labeling that claims production in a small geographic region is critical to traceability, quality control and brand protection. In the current study, isotope ratio mass spectrometry (IRMS) was used to generate profiles of δ13 C and δ15 N to determine if the stable isotope signatures of Keemun black tea differ within the three counties that claim production. Other factors (cultivar type, leaf maturity and manufacturing process) were considered for their potential effects. RESULTS: Both cultivar type and leaf maturity have remarkable impact on the δ15 N values of tea leaves, and that the cultivar influenced the δ13 C values. Keemun black tea from Qimen county could be easily discriminated from samples from Dongzhi and Guichi counties based on δ15 N signatures. The k-NN model was cross-validated with an accuracy of 91.6%. Environmental factors and/or genotype seem to be the major reasons for δ15 N differences in Keemun black tea from the selected regions. CONCLUSION: This article provides a potential effective method to delineate the geographic point-of-origin of Keemun black tea based on δ15 N signatures. © 2018 Society of Chemical Industry.

Real-Time and in Situ Monitoring of Pesticide Penetration in Edible Leaves by Surface-Enhanced Raman Scattering Mapping.

Understanding of the penetration behaviors of pesticides in fresh produce is of great significance for effectively applying pesticides and minimizing pesticide residues in food. There is lack, however, of an effective method that can measure pesticide penetration. Herein, we developed a novel method for real-time and in situ monitoring of pesticide penetration behaviors in spinach leaves based on surface-enhanced Raman scattering (SERS) mapping. Taking advantage of penetrative gold nanoparticles (AuNPs) as probes to enhance the internalized pesticide signals in situ, we have successfully obtained the internal signals from thiabendazole, a systemic pesticide, following its penetration into spinach leaves after removing surface pesticide residues. Comparatively, ferbam, a nonsystemic pesticide, did not show internal signals after removing surface pesticide residues, demonstrating its nonsystemic behavior. In both cases, if the surface pesticides were not removed, copenetration of both AuNPs and pesticides was observed. These results demonstrate a successful application of SERS as an effective method for measuring pesticides penetration in fresh produce in situ. The information obtained could provide useful guidance for effective and safe applications of pesticides on plants.

Alteration of the Nonsystemic Behavior of the Pesticide Ferbam on Tea Leaves by Engineered Gold Nanoparticles.

A model system consisting of a nonsystemic pesticide (ferbam), engineered gold nanoparticles (AuNPs) and a plant tissue (tea leaves) was investigated using surface enhanced Raman spectroscopy (SERS). Ferbam has no ability by itself to penetrate into tea leaves. When AuNPs were placed with ferbam onto the surface of tea leaves, however, the SERS signal of the ferbam-AuNPs complex was observed inside of the tea leaves. Within 1 h, the ferbam-AuNPs complex rapidly penetrated into the leaf to a depth of approximately 190 µm, about (1)/3 to (1)/2 of the leaf's thickness. The rate of penetration was dependent on the size of AuNPs, with 30 nm AuNPs-ferbam penetrating more rapidly when compared with complexes made with the 50 and 69 nm AuNPs. These results clearly demonstrated an alteration of the nonsystemic behavior of ferbam in the combined presence with AuNPs. This finding might lead to the development of some new pesticide formulations. Conversely, new toxicity issues may arise as the behaviors and fate of pesticides are altered significantly upon interaction with engineered NPs in the pesticide formulation or environment.

Two New Oleanane-Type Saponins with Anti-Proliferative Activity from Camellia oleifera Abel. Seed Cake.

Two new oleanane-type saponins, named oleiferasaponins C4 (1) and C5 (2), were isolated from Camellia oleifera Abel. seed cake residue. Their respective structures were identified as 16α-hydroxy-22α-O-angeloyl-23α-aldehyde-28-dihydroxymethylene-olean-12-ene-3ß-O-[ß-d-galacto-pyranosyl-(1→2)]-[ß-d-glucopyranosyl-(1→2)-ß-d-galactopyranosy-(1→3)]-ß-d-glucopyranosid-uronic acid methyl ester (1) and 16α-hydroxy-22α-O-angeloyl-23α-aldehyde-28-dihydroxy-methylene-olean-12-ene-3ß-O-[ß-d-galactopyranosyl-(1→2)]-[ß-d-galactopyranosyl-(1→3)]-ß-d-glucopyranosiduronic acid methyl ester (2) through 1D- and 2D-NMR, HR-ESI-MS, and GC-MS spectroscopic methods. The two compounds exhibited potent cytotoxic activities against five human tumor cell lines (BEL-7402, BGC-823, MCF-7, HL-60 and KB).

Rapid, in-situ evaluation of sunflower seed freshness and vigor using Raman microspectroscopy scanning of carotenoids.

An ultra-rapid, in-situ Raman microscopy strategy was developed for judging both seed freshness and seed vigor based on relative quantification of carotenoids content during sunflower seed germination. The carotenoids content was determined using the ratio of the Raman peak intensities at 1525 and 1268 cm-1 (I1525/1268). When different samples (harvest times and storage conditions) were soaked in water for 0-24 h, the carotenoids content in the embryonic axes gradually increased, with the carotenoids higher in fresher seeds. Using this method, freshly harvested sunflower seeds (2022) were successfully discriminated from seeds harvested over three previous years (2019-2021) and from seeds subjected to accelerated aging at 45 °C or 60 °C for 2-8 days, the samples were correctly differentiated >90%. In addition, a linear correlation between I1525/1268 ratio and seed germination was found (R2 > 0.95). This proposed method can serve as an ultra-rapid strategy for determination of sunflower seed quality.

Tea's Characteristic Components Eliminate Acrylamide in the Maillard Model System.

This study investigated the effects of various characteristic components of tea-theaflavins, catechins, thearubigins, theasinensins, theanine, catechin (C), catechin gallate (CG), epicatechin (EC), epicatechin gallate (ECG), epigallocatechin (EGC), epigallocatechin gallate (EGCG), gallocatechin (GC), and gallocatechin gallate (GCG)-on acrylamide formation. The results revealed that most of tea's characteristic components could significantly eliminate acrylamide, ranked from highest to lowest as follows: GC (55.73%) > EC (46.31%) > theaflavins (44.91%) > CG (40.73%) > thearubigins (37.36%) > ECG (37.03%) > EGCG (27.37%) > theabrownine (22.54%) > GCG (16.21%) > catechins (10.14%) > C (7.48%). Synergistic elimination effects were observed with thearubigins + EC + GC + CG, thearubigins + EC + CG, thearubigins + EC + GC, theaflavins + GC + CG, and thearubigins + theaflavins, with the reduction rates being 73.99%, 72.67%, 67.62%, 71.03%, and 65.74%, respectively. Tea's components reduced the numbers of persistent free radicals to prevent acrylamide formation in the model system. The results provide a theoretical basis for the development of low-acrylamide foods and the application of tea resources in the food industry.

Zirconium­cerium modified polyvinyl alcohol/NaCMC biocomposite film: Synthesis of films through high-speed shear assisted technique and removal fluoride from water.

A new zirconium and cerium-modified polyvinyl alcohol (PVA) sodium carboxymethyl cellulose (NaCMC) film (PVA/CMC-Zr-Ce) was synthesized thru a high-speed shear-assisted method and its adsorption for the removal of fluoride was studied, in which the NaCMC provided -COONa for ion exchange between Na and Zr-Ce, thus the loading amount of Zr-Ce on films was accordingly increased. The morphology and structure of PVA/CMC-Zr-Ce were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Besides, the mechanical properties, water contact angle, and swelling ratio of film were also evaluated. The addition of high-speed shear improved the dispersion of the emulsion system, and PVA/CMC-Zr-Ce film with good adsorption performance and film stability was prepared. While, it was found that the adsorption capacity could reach 67.25 mg/g and equilibrium time could reach 20 min. The adsorption mechanism of PVA/CMC-Zr-Ce revealed that ion exchange between hydroxide and fluoride, electrostatic interactions and complexation were the dominating influencing factors. Based on these findings, it can be concluded that PVA/CMC-Zr-Ce film- synthesized with high-speed shear assistance technique is a promising adsorbent for fluoride removal from water.

A novel fluorescent and photothermal probe based on nanozyme-mediated cascade reaction for detecting organophosphorus pesticide residues.

In this study, a nanozyme (ZIF-Co-Cys) with high oxidase-like catalytic activity was prepared, and a ratiometric fluorescent/photothermal dual-mode probe was constructed for organophosphorus pesticides (OPs) detection based on the competitive effect of ZIF-Co-Cys and the enzymatic reaction product of acid phosphatase (ACP) on o-phenylenediamine and the inhibition effect of OPs on ACP activity. Using dimethyl dichloroviny phosphate (DDVP) as the model, both the fluorescence intensity ratio and the temperature change of the probe solution exhibited an excellent correlation with OPs concentration. The detection limits were 1.64 ng/mL and 0.084 ng/mL, respectively. Additionally, the detection of DDVP residues in real samples verified the outstanding anti-interference and accuracy of the probe. This work not only provided a complementary dual-mode method for the accurate and rapid detection of OPs residues in complex samples, but also supplied a new insight into the design of a multi-mode sensing platform based on the cascade reaction of nanozyme.

Mn-modified porphyrin metal-organic framework mediated colorimetric and photothermal dual-channel probe for sensitive detection of organophosphorus pesticides.

Herein, a novel dual-mode probe for organophosphorus pesticides (OPs) colorimetric and photothermal detection was developed based on manganese modified porphyrin metal-organic framework (PCN-224-Mn). PCN-224-Mn had excellent oxidase-like activity and oxidized colorless 3,3,5,5-tetramethylbenzidine (TMB) to blue-green oxidation state TMB (oxTMB), which exhibited high temperature under near-infrared irradiation. l-ascorbate-2-phosphate was hydrolyzed by acid phosphatase to produce ascorbic acid, which weakened colorimetric and photothermal signals by impacting oxTMB generation. The presence of OPs blocked the production of ascorbic acid by irreversibly inhibiting the activity of acid phosphatase, causing the restoration of chromogenic reaction and the increase of temperature. Under the optimal conditions, the probe showed a good linear response to OPs in the concentration range of 5 âˆ¼ 10000 ng/mL, using glyphosate as the analog. The detection limits of glyphosate in colorimetric mode and photothermal mode were 1.47 ng/mL and 2.00 ng/mL, respectively. The probe was successfully used for sensitive identification of OPs residues in tea, brown rice, and wheat flour. This work proposes a simple and reliable colorimetric/photothermal platform for OPs identification, which overcomes the problem that single-mode detection probes are susceptible to external factors, and has broad application potential in the field of food safety.