Nitro fatty acids: A comprehensive review on analytical methods and levels in health and disease.

Nitro fatty acids (NO2-FAs) are biologically active compounds produced from the reaction of unsaturated fatty acids with reactive nitrogen species (RNS). Due to their electrophilic nature, these endogenously produced metabolites can react with nucleophilic targets, producing a spectrum of modulatory and protective effects. Determination of NO2-FAs in biological samples is challenging due to their low nanomolar to picomolar endogenous concentrations, indistinct metabolism, and distribution in many tissues and biofluids. Several attempts have been made to develop precise, standardized, and efficient methodologies for assessing physiological and pathophysiological processes to overcome the difficulties associated with their measurement. This review discusses those approaches utilizing liquid chromatography tandem mass spectrometry (LC‒MS/MS) and gas chromatography tandem mass spectrometry (GC‒MS/MS) for the quantification of NO2-FAs, in addition to a summary of their laboratory synthesis and extraction from biological samples. Clinical associations with different pathological conditions, including hyperlipidaemia, cardiac ischemia and herpes simplex type 2 viral infection (HSV-2), are also discussed.

Persistence of pesticide residues in weathered avian droppings.

Avian droppings (combination of fecal matter and urates) provide a non-lethal and non-invasive matrix for measuring pesticide exposures. In the field, droppings may be collected days or weeks after excretion and the persistence of pesticide residues in weathered droppings is not known. Thus, we studied the effects of weathering on pesticide residues in droppings. Domestic chicken (Gallus gallus domesticus) hens were used as a representative species for Order Galliformes. We collected droppings from hens before they were exposed to the pesticides (reference or pre-dose droppings ). Thereafter, the hens were orally administered encapsulated wheat seeds coated with Raxil® PRO Shield (containing the active ingredients imidacloprid, prothioconazole, metalaxyl, and tebuconazole) for consecutive 7 days. During this time, their droppings were collected on days 3, 5, and 8 from the start of the exposure period (post-dose droppings ). The pre-dose and post-dose droppings were weathered for up to 30 days in autumn and spring in shrubsteppe habitat. Droppings were analyzed using HPLC coupled to triple quad LC/MS for parent compound and metabolite residues. No pesticide or its metabolite residues were detected in the weathered reference droppings. No parent pesticide compounds were detected in weathered post-dose droppings but imidacloprid metabolites, imidacloprid-5-hydroxy and imidacloprid-olefin, and the prothioconazole metabolite, desthio-prothioconazole, were detected in all post-dose weathered samples from both seasons. The active ingredients metalaxyl and tebuconazole and their metabolites were not detected in any of the samples. Our results suggest that, depending on the pesticide, its concentration, and the environmental conditions, residues of some pesticides can be detected in droppings weathered for at least 30 days. Knowledge of pesticide persistence in weathered droppings can help refine the quality and quantity of fecal samples that are collected for monitoring pesticide exposures to birds.

Fluorometric detection of copper and imidacloprid using nitrogen-doped graphitic carbon dots: A promising method for environmental monitoring.

Pesticides in environmental samples pose significant risks to ecosystems and human health since they require precise and efficient detection methods. Imidacloprid (IMI), a widely used neonicotinoid insecticide, exemplifies these hazards due to its potential toxicity. This study addresses the urgent need for improved monitoring of such contaminants by introducing a novel fluorometric method for detecting IMI using nitrogen-doped graphite carbon dots (N-GCDs). The sensor operates by quenching fluorescence through the interaction of Cu2+ ions with N-GCDs. Subsequently, IMI binds to the imidazole group, chelates with Cu2+, and restores the fluorescence of N-GCDs. This alternating fluorescence behavior allows for the accurate identification of both Cu2+ and IMI. The sensor exhibits linear detection ranges of 20-100 nM for Cu2+ and 10-140 µg/L for IMI, with detection limits of 18 nM and 1.2 µg/L, respectively. The high sensitivity of this sensor enables the detection of real-world samples, which underscores its potential for practical use in environmental monitoring and agricultural safety.

Nitazene test strips: a laboratory evaluation.

BACKGROUND: 2-Benzylbenzimidazole 'nitazene' opioids pose a growing threat to public health. Nitazene analogues are increasingly found mixed with or (mis)sold as heroin and in falsified (non-)opioid medications, posing a great risk of intoxication in users (un)knowingly exposed to these potent opioids. Lateral flow immunoassay nitazene test strips (NTS; BTNX Rapid Response™) became commercially available in Q1 2024, with the aim to enable rapid detection of nitazene analogues in drug samples. As only limited independent data is available on the performance of these strips, this lab-based study aimed at evaluating their potential for drug checking applications. METHODS: Following dilution of drug standards in water, the NTS readouts were analyzed independently by two individuals and by ImageJ. The limit of detection for isotonitazene was determined using two manufacturing lots of NTS. Cross-reactivity with 32 other nitazene analogues was evaluated. Six sourced drug samples were tested to explore the ability of NTS to detect the presence of a nitazene analogue in authentic samples. RESULTS: The limits of detection for isotonitazene were 2000 or 3000 ng/mL, depending on the lot. Twenty-four of the 33 tested nitazene analogues cross-reacted with the NTS at concentrations ≤ 9000 ng/mL. Structural analysis indicated that either substitution or removal of the 5-nitro group, or lengthening the linker between the two aromatic rings, generally hampered detection. All six authentic drug samples consistently tested positive, with no observed false negatives. CONCLUSIONS: This study provides a better understanding of the potential of NTS for drug checking purposes. Our findings indicate that NTS can theoretically alert to the presence of most nitazene analogues that have emerged on recreational drug markets. However, 'desnitazenes' (lacking the 5-nitro group) may yield false negative results due to low cross-reactivity. Although factors like specificity, lot-to-lot variability, nitazene analogue content in drug samples, solubility, and different testing conditions should be considered, our study results indicate that, at least under the conditions evaluated here (using reference standards and sourced powders), NTS are capable of detecting the presence of a wide range of nitazene analogues. Hence, NTS may alert users of the presence of nitazene analogues in drug samples.

Kill two birds with one stone: colorimetric/fluorescence immunosensor based on Au@Pt nanozyme for sensitive detection of imidacloprid.

Gold-platinum (Au@Pt) nanozymes with high catalytic activity and stability were designed to improve the stability of the enzyme-linked immunosorbent assay (ELISA), and a two-mode signal output was used to enhance the sensitivity and confidence of the assay. This study reports the two-mode signal output based on Au@Pt nanozyme to catalyzed 3,3',5,5'-tetramethylbenzidine (TMB) reaction. Oxidized 3,3',5,5'-tetramethylbenzidine (ox-TMB) has wide absorption spectrum, providing excellent optical density capabilities and fluorescence quenching. The detection limits of imidacloprid were 0.88 µg/L and 1.14 µg/L in colorimetric and fluorescence modes, respectively. Multiple-mode strategy improves detection accuracy, increases the confidence of experimental results, and broadens detection modes. Two modes can meet the requirements of accurate and flexible multi-mode sensing in different application situations.

Characterization of near-field temporal and spatial variations of pesticide residues using honeybee specimens as bio-sensing matrices.

This study was prompted by recent reports of the ubiquity of neonicotinoids (neonics) in environment and the likelihood of exposures and health hazards to non-target organisms. We aimed to quantify neonics levels in time- and location-match pollen and nectar samples foraged by honeybees (Apis mellifera) and characterized the temporal and spatial variations using a relative potency factor method to determine the total neonic levels, expressed as the imidacloprid-adjusted total neonics, IMIRPF (ng/g). Six pairs of pollen and nectar samples, a total of twelve samples, were collected from each of the thirty-two experimental hives during the active foraging months of March, April, and June and analyzed for eight neonics. We found 59% and 64% of pollen and nectar contained at least one neonic, respectively. Among those neonic-detected pollen and nectar samples, 45% and 77% of them contained more than one neonic, respectively. Imidacloprid and acetamiprid in pollen and clothianidin and thiamethoxam in nectar accounted for 60% and 83% detection, respectively. The highest 3-month average of IMIRPF in pollen (6.56 ng/g) and nectar (11.19 ng/g) were detected in a location with the predominant production of citrus fruit. The temporal and spatial variations of IMIRPF levels demonstrated the robustness of using paired pollen and nectar data as the bio-sensing matrices to facilitate the assessment of near-field exposure to total neonics and the delineation of risks.

Multi-omics approach reveals elevated potential of bacteria for biodegradation of imidacloprid.

The residual imidacloprid, a widely used insecticide is causing serious environmental concerns. Knowledge of its biodegradation will help in assessing its residual mass in soil. In view of this, a soil microcosm-based study was performed to test the biodegradation potential of Agrobacterium sp. InxBP2. It achieved ∼88% degradation in 20 days and followed the pseudo-first-order kinetics (k = 0.0511 day-1 and t1/2=7 days). Whole genome sequencing of Agrobacterium sp. InxBP2 revealed a genome size of 5.44 Mbp with 5179 genes. Imidacloprid degrading genes at loci K7A42_07110 (ABC transporter substrate-binding protein), K7A42_07270 (amidohydrolase family protein), K7A42_07385 (ABC transporter ATP-binding protein), K7A42_16,845 (nitronate monooxygenase family protein), and K7A42_20,660 (FAD-dependent monooxygenase) having sequence and functional similarity with known counterparts were identified. Molecular docking of proteins encoded by identified genes with their respective degradation pathway intermediates exhibited significant binding energies (-6.56 to -4.14 kcal/mol). Molecular dynamic simulation discovered consistent interactions and binding depicting high stability of docked complexes. Proteome analysis revealed differential protein expression in imidacloprid treated versus untreated samples which corroborated with the in-silico findings. Further, the detection of metabolites proved the bacterial degradation of imidacloprid. Thus, results provided a mechanistic link between imidacloprid and associated degradative genes/enzymes of Agrobacterium sp. InxBP2. These findings will be of immense significance in carrying out the lifecycle analysis and formulating strategies for the bioremediation of soils contaminated with insecticides like imidacloprid.

Low doses of the neonicotinoid insecticide imidacloprid induce ROS triggering neurological and metabolic impairments in Drosophila.

Declining insect population sizes are provoking grave concern around the world as insects play essential roles in food production and ecosystems. Environmental contamination by intense insecticide usage is consistently proposed as a significant contributor, among other threats. Many studies have demonstrated impacts of low doses of insecticides on insect behavior, but have not elucidated links to insecticidal activity at the molecular and cellular levels. Here, the histological, physiological, and behavioral impacts of imidacloprid are investigated in Drosophila melanogaster, an experimental organism exposed to insecticides in the field. We show that oxidative stress is a key factor in the mode of action of this insecticide at low doses. Imidacloprid produces an enduring flux of Ca2+ into neurons and a rapid increase in levels of reactive oxygen species (ROS) in the larval brain. It affects mitochondrial function, energy levels, the lipid environment, and transcriptomic profiles. Use of RNAi to induce ROS production in the brain recapitulates insecticide-induced phenotypes in the metabolic tissues, indicating that a signal from neurons is responsible. Chronic low level exposures in adults lead to mitochondrial dysfunction, severe damage to glial cells, and impaired vision. The potent antioxidant, N-acetylcysteine amide (NACA), reduces the severity of a number of the imidacloprid-induced phenotypes, indicating a causal role for oxidative stress. Given that other insecticides are known to generate oxidative stress, this research has wider implications. The systemic impairment of several key biological functions, including vision, reported here would reduce the resilience of insects facing other environmental challenges.

Changing on the Concentrations of Neonicotinoids in Rice and Drinking Water through Heat Treatment Process.

Neonicotinoids (NEOs) have become the most widely used insecticides in the world since the mid-1990s. According to Chinese dietary habits, rice and water are usually heated before being consumed, but the information about the alteration through the heat treatment process is very limited. In this study, NEOs in rice samples were extracted by acetonitrile (ACN) and in tap water, samples were extracted through an HLB cartridge, then, a high-performance liquid chromatography system and a triple quadrupole mass spectrometry (HPLC-MS/MS) were applied for target chemical analysis. The parents of NEOs (p-NEOs) accounted for >99% of the total NEOs mass (∑NEOs) in both uncooked (median: 66.8 ng/g) and cooked (median: 41.4 ng/g) rice samples from Guangdong Province, China, while the metabolites of NEOs (m-NEOs) involved in this study accounted for less than 1%. We aimed to reveal the concentration changes of NEOs through heat treatment process, thus, several groups of rice and water samples from Guangdong were cooked and boiled, respectively. Significant (p < 0.05) reductions in acetamiprid, imidacloprid (IMI), thiacloprid, and thiamethoxam (THM) have been observed after the heat treatment of the rice samples. In water samples, the concentrations of THM and dinotefuran decreased significantly (p < 0.05) after the heat treatment. These results indicate the degradation of p-NEOs and m-NEOs during the heat treatment process. However, the concentrations of IMI increased significantly in tap water samples (p < 0.05) after heat treatment process, which might be caused by the potential IMI precursors in those industrial pesticide products. The concentrations of NEOs in rice and water can be shifted by the heat treatment process, so this process should be considered in relevant human exposure studies.

Chemical composition, sources and optical properties of nitrated aromatic compounds in fine particulate matter during winter foggy days in Nanjing, China.

Functionalized aromatic compounds are one of the most important light-absorbing organic chromophores - so-called brown carbon (BrC) - in fine particulate matter (PM2.5). In this study, we conducted a wintertime field campaign to measure eight nitrated aromatic compounds (NACs) in PM2.5 with offline analysis techniques, including liquid chromatograph mass spectrometer (LC-MS) and aerodyne high-resolution aerosol mass spectrometer (AMS) measurements, during foggy and nonfoggy days in suburban Nanjing in the Yangtze River Delta region, China. On average, 4-nitrophenol could be one of the most important light absorbing materials in the observed BrC, which accounted for over 40% of the mass concentration of identified chromophores. The mass concentration of 2-methyl-4-nitrophenol and 2,6-dimethyl-4-nitrophenol were evidently increased during foggy days, contribution of which to total NACs were increased by 10% and 5%, respectively. Positive matrix factorization analysis of combining LC-MS and AMS dataset was performed to identify the primary and secondary sources of NACs. Primary sources, e.g., traffic and solid-fuel combustion, accounted for 71% of the sum of 4-nitrophenol, 2,6-dimethyl-4-nitrophenol and 3-nitrosalicylic acid, suggesting important contribution of primary emissions to these NACs. The contribution of secondary sources, associated with two oxygenated organic aerosols, could contribute 66% to 4-nitrophenol, reflecting the link of such nitrated aromatic compounds to secondary organic aerosol source. Together with optical measurements, 4-nitrophenol presented a high contribution (>50%) to the identified BrC absorbance in the light range 250 and 550 nm was observed. This could highlight an important role of such NACs in ambient BrC light absorption, despite its mass contribution to total organic carbon was negligible. Our work could improve the understanding of the links between optical properties and chemical composition of BrC, and the difference between BrC chromophores from nonfoggy days and foggy days under the typical polluted atmospheric conditions.

Trace determination of imidacloprid and its major metabolites in wheat-soil system.

Trace analysis method is a reliable basis for studying the translocation and metabolism of imidacloprid used as an insecticide in wheat, and it clarifies whether biologically active metabolites including residual imidacloprid, have long-lasting insecticidal potency against wheat aphids under seed treatment during the entire growth period. In this study, a highly sensitive analytical method was established to determine the residues of imidacloprid and its six metabolites (5-hydroxy imidacloprid, imidacloprid olefin, imidacloprid guanidine, imidacloprid urea, 6-chloronicotinic acid, and imidacloprid nitrosimine) in wheat-soil systems, such as in wheat leaves, wheat ears, wheat grains, roots, and soil. All the compounds were extracted using an ACN:water (8:2, v/v) mixture and purified by dispersive solid-phase extraction. The average recoveries ranged from 74.4% to 109.5% for all matrices, with intra- and inter-day variations of less than 14.9%. The limit of quantitation was in the range of 0.001-0.005 mg/kg. The method is demonstrated to be sensitive and accurate for monitoring imidacloprid and its metabolites at trace levels during the entire growth period under field conditions.

Residual levels and dietary risk assessment of bifenthrin and dinotefuran and its major metabolites in open wheat field conditions.

To evaluate the residual levels of bifenthrin and dinotefuran, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-tandem mass spectrometry method for simultaneous detection of bifenthrin and dinotefuran and its major metabolites in wheat was developed and validated. Dietary risk assessments were further performed based on the relevant residual data from 12 wheat fields, toxicology data and dietary patterns. In wheat grain and straw, the recoveries of all analytes ranged from 77 to 102% with the relative standard deviation <9.7% and the limit of quantitation 0.05 mg kg-1 . The highest terminal residue of bifenthrin in wheat grain was 0.069 mg kg-1 and dinotefuran was 0.34 mg kg-1 . Residual concentrations of bifenthrin and dinotefuran decreased to <0.05 and 0.15 mg kg-1 at 21 days (pre-harvest interval), respectively. The chronic risk quotient ranged from 6.4 to 62.7% and the acute risk quotient varied from 0.38 to 17.73%. The chronic and acute dietary risks caused by the terminal residues of the two insecticides were negligible for Chinese populations. The recommended pre-harvest interval was proposed to ensure safe wheat consumption. These data could provide a scientific reference to establish the Chinese maximum residue limit of dinotefuran in wheat.

Bees prefer foods containing neonicotinoid pesticides.

The impact of neonicotinoid insecticides on insect pollinators is highly controversial. Sublethal concentrations alter the behaviour of social bees and reduce survival of entire colonies. However, critics argue that the reported negative effects only arise from neonicotinoid concentrations that are greater than those found in the nectar and pollen of pesticide-treated plants. Furthermore, it has been suggested that bees could choose to forage on other available flowers and hence avoid or dilute exposure. Here, using a two-choice feeding assay, we show that the honeybee, Apis mellifera, and the buff-tailed bumblebee, Bombus terrestris, do not avoid nectar-relevant concentrations of three of the most commonly used neonicotinoids, imidacloprid (IMD), thiamethoxam (TMX), and clothianidin (CLO), in food. Moreover, bees of both species prefer to eat more of sucrose solutions laced with IMD or TMX than sucrose alone. Stimulation with IMD, TMX and CLO neither elicited spiking responses from gustatory neurons in the bees' mouthparts, nor inhibited the responses of sucrose-sensitive neurons. Our data indicate that bees cannot taste neonicotinoids and are not repelled by them. Instead, bees preferred solutions containing IMD or TMX, even though the consumption of these pesticides caused them to eat less food overall. This work shows that bees cannot control their exposure to neonicotinoids in food and implies that treating flowering crops with IMD and TMX presents a sizeable hazard to foraging bees.

Dissipation of imidacloprid and its metabolites in Chinese prickly ash (Zanthoxylum) and their dietary risk assessment.

Dissipation of imidacloprid (IMI) and its metabolites (urea, olefin, 5-hydroxy, guanidine, 6-chloronicotinic acid) in Chinese prickly ash (CPA) was investigated using QuEChERS combined with UPLC-MS/MS. Good linearity (r2 ≥0.9963), accuracy (recoveries of 71.8-104.3%), precision (relative standard deviations of 0.9-9.4%), and sensitivity (limit of quantification ≤0.05 mg kg-1) were obtained. After application of IMI at dosage of 467 mg a.i. L-1 for three times with interval of 7 d, the dissipation dynamics of IMI in CPA followed first-order kinetics, with half-life of 6.48-7.29 d. IMI was the main compound in CPA, followed by urea and guanidine with small amounts of olefin, 5-hydroxy, and 6-chloronicotinic acid. The terminal residues of total IMI and its metabolites at PHI of 14-21 d were 0.16-7.80 mg kg-1 in fresh CPA and 0.41-10.44 mg kg-1 in dried CPA, with the median processing factor of 3.62. Risk assessment showed the acute (RQa) and chronic dietary risk quotients (RQc) of IMI in CPA were 0.020-0.083% and 0.052-0.334%, respectively. Based on the dietary structures of different genders and ages of Chinese people, the whole dietary risk assessment indicated that RQc was less than 100% for the general population except for 2- to 7-year-old children (RQc of 109.9%), implying the long-term risks of IMI were acceptable to common consumers except for children.

Responses of Aquatic Nontarget Organisms in Experiments Simulating a Scenario of Contamination by Imidacloprid in a Freshwater Environment.

Several studies have indicated the presence of the neonicotinoid insecticide imidacloprid (IMI) in aquatic ecosystems in concentrations up to 320.0 µg L-1. In the present study, we evaluated the effects of the highest IMI concentration detected in surface water (320.0 µg L-1) on the survival of Chironomus sancticaroli, Daphnia similis, and Danio rerio in three different scenarios of water contamination. The enzymatic activities of glutathione S-transferase (GST), catalase (CAT), and ascorbate peroxidase (APX) in D. rerio also were determined. For this evaluation, we have simulated a lotic environment using an indoor system of artificial channels developed for the present study. In this system, three scenarios of contamination by IMI (320.0 µg L-1) were reproduced: one using reconstituted water (RW) and the other two using water samples collected in unpolluted (UW) and polluted (DW) areas of a river. The results indicated that the tested concentration was not able to cause mortality in D. similis and D. rerio in any proposed treatment (RW, UW, and DW). However, C. sancticaroli showed 100% of mortality in the presence of IMI in the three proposed treatments, demonstrating its potential to impact the community of aquatic nontarget insects negatively. Low IMI concentrations did not offer risks to D. rerio survival. However, we observed alterations in GST, CAT, and APX activities in treatments that used IMI and water with no evidence of pollution (i.e., RW and UW). These last results demonstrated that fish are more susceptible to the effects of IMI in unpolluted environments.

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions.

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg-1), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.

Relationship between imidacloprid residues and control effect on cotton aphids in arid region.

In this case, the dissipation and residues of imidacloprid as well as its control efficacy against aphids (Aphis gossypii Glover) in cotton cropping system were reported. After the final spray at the rates of 10.5-42.5 g a.i. ha-1, the initial deposits were 0.59-2.25 mg kg-1 with half-lives of 2.12-2.84 days on leaves and 0.06-0.21 mg kg-1 with half-lives of 1.51-4.20 days in soil, respectively. The initial residues were significantly higher with longer persistence in the upper position of the leaf than in middle and lower positions. The different application dosages could induce a significant difference in the initial deposits, but not show consistent correlation with the dissipation rate. The repeated applications of imidacloprid could alter its residue levels and dissipation rates. The long-term residue concentrations of imidacloprid (60 days after the final application) reached to the nondetectable level in soil. Combined with the control efficacy results, it was considered that the recommended dose of imidacloprid on cotton could be used effectively and safe in this arid area from the view of crop protection and environmental contamination.

A pH-Sensing Fluorescent Metal-Organic Framework: pH-Triggered Fluorescence Transition and Detection of Mycotoxin.

Due to its great relevance to environmental, biological, and chemical processes, the precise detection of pH or acidic/basic species is an ongoing and imperative need. In this context, pH-sensitive luminescent systems are highly desired. We reported a three-dimensional Zn(II) MOF synthesized from a bipyridyl-tetracarboxylic ligand and composed of 4-fold interpenetrated diamond frameworks. Because the steric hindrance in the ligand prevents metal coordination with the pyridyl group, the MOF features free basic N sites accessible to the small H+ ions, which renders pH responsivity. The aqueous dispersion exhibits an abrupt, high-contrast, and reversible on-off fluorescence transition in the narrow pH range of 5.4-6.2. The sensitive bistable system can be used for the precise monitoring of pH within the range and for use as a pH-triggered optical switch. The responsive mechanism through pyridyl protonation is collaboratively supported by data fitting, absorption spectra, and molecular orbital calculations. In particular, spectral and theoretical analyses reveal the destruction of n → π* transitions and the appearance of intramolecular charge-transfer transitions upon pyridyl protonation. Moreover, by virtue of the pH-responsive fluorescence, the MOF shows appealing sensing performance for the detection of 3-nitropropionic acid, a major mycotoxin in moldy sugar cane.

Capillary liquid chromatography as an effective method for the determination of seven neonicotinoid residues in honey samples.

A new analytical method based on capillary liquid chromatography with diode array detection has been developed for the simultaneous quantification of seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) in honey samples. The separation was achieved in a Zorbax XDB-C18 column (150 × 0.5 mm id, 5 µm), with a mobile phase consisting of ultrapure water (solvent A) and acetonitrile (solvent B) at a flow rate of 10 µL/min. Capillary column was thermostated at 25°C during the analysis and 254 or 270 nm was established as detection wavelength, depending on the analyte. Furthermore, full loop injection mode (8 µL) was selected, using water as injection solvent. Finally, the optimized method was applied to the analysis of neonicotinoid residues in honey of different floral origins using dispersive liquid-liquid microextraction as sample treatment. Variables affecting the extraction efficiency were optimized, choosing methanol and dichloromethane as dispersive and extraction solvents, respectively. The method was characterized in terms of linearity ( R 2 ≥ 0.9948), repeatability, reproducibility (relative standard deviation below 4.5 and 6.3% respectively), and recoveries (≥80.5%). Detection and quantification limits were lower than 6.6 and 22.0 µg/kg for the studied analytes, respectively.

Degradation of imidacloprid by UV-activated persulfate and peroxymonosulfate processes: Kinetics, impact of key factors and degradation pathway.

UV-activated persulfate (UV/PS) and peroxymonosulfate (UV/PMS) processes as alternative methods for removal of imidacloprid (IMP) were conducted for the first time. The reaction rate constants between IMP and the sulfate or hydroxyl radical were calculated as 2.33×109  or 2.42×1010 M-1 s-1, respectively. The degradation of IMP was greatly improved by UV/PS and UV/PMS compared with only UV or oxidant. At any given dosage, UV/PS achieved higher IMP removal rate than UV/PMS. The pH range affecting the degradation in the UV/PS and UV/PMS systems were different in the ranges of 6-8 and 9 to 10. SO42-, F- and NO3- had no obvious effect on the degradation in the UV/PS and UV/PMS systems. CO32- and PO43- inhibited the degradation of IMP in the UV/PS system, while they enhanced the degradation in the UV/PMS system. Algae organic matters (AOM) were used to consider the impact of the degradation of IMP for the first time. The removal of IMP were restrained by both AOM and natural organic matters. The higher removal rate of IMP demonstrated that both UV/PS and UV/PMS were suitable for treating the water containing IMP, while UV/PS was cost-effective than UV/PMS based on the total cost calculation. Finally, the degradation pathways of IMP were proposed.