Enhanced detection of 4-nitrophenol in drinking water: ECL sensor utilizing velvet-like graphitic carbon nitride and molecular imprinting.

In this work, a molecularly imprinted electrochemiluminescence (ECL) sensor was developed for selective detection of 4-nitrophenol (4-NP) in drinking water for the first time. By synthesizing velvet-like graphitic carbon nitride (V-g-C3N4) via one-step thermal polycondensation and integrating it with a molecularly imprinted polymer (MIP), the ECL sensor was fabricated. The MIP-modified V-g-C3N4 composites (MIP/V-g-C3N4) were synthesized using a sol-gel method with 4-NP as the template molecule. Under optimal conditions, the ECL sensor exhibited a wide detection range (5 × 10-10-1 × 10-5 mol/L) and a low detection limit (1.8 × 10-10 mol/L). In testing with actual drinking water samples, it displayed high accuracy (recoveries for intraday and inter-day: 93.50-106.2% and 97.00-107.3%, separately) and precision (RSDs for intraday and inter-day: 1.54-4.59% and 1.53-4.28%, respectively). The developed MIP-based ECL sensor demonstrated excellent selectivity, stability, and reproducibility, offering a promising and reliable approach for highly sensitive and selective determination of 4-NP in drinking water.

Microwave-assisted preparation of yellow fluorescent graphitic carbon nitride quantum dots for trace tetracycline-specific detection.

Tetracycline (TC) is extensively utilized in livestock breeding, aquaculture, and medical industry. TC residues seriously harm food security, the environment, and human health. There is an urgent need to exploit a highly efficient and sensitive testing method to monitor TC residue levels in aquatic environments. In this study, graphitic carbon nitride quantum dots (g-CNQDs) were successfully synthesized by a one-step microwave-assisted method using citric acid and urea as precursors. The as-prepared g-CNQDs with size of 1.25-3.75 nm exhibited bright yellow fluorescence at 523 nm when excited at 397 nm. Interestingly, this characteristic fluorescence emission of g-CNQDs could be selectively and efficiently quenched by TC. Based on this phenomenon, for TC detection was successfully explored and applied in real water samples. Wide linear scope of 7-100 µM, low detection limit (LOD) of 0.48 µM, satisfactory recovery of 97.77%-103.4%, and good relative standard deviation (RSD) of 1.05-5.87% were obtained. Mechanism investigations revealed that the static quenching and the inner filter effect (IFE) were responsible for this fluorescence quenching between g-CNQDs and TC. This work not only provided a facile approach for g-CNQDs synthesis but also constructed a g-CNQDs-based fluorescent sensor platform for the highly sensitive and selective detection of TC in aquatic environments.

Dissipation kinetics and the evaluation of dietary risks associated with deltamethrin, ethion, fenazaquin, and fenpropathrin on bell pepper (Solanum annuum L.).

Bell peppers, a globally significant crop, face infestations from various pests. In a study, bell peppers were treated with deltamethrin, ethion, fenazaquin, and fenpropathrin at recommended and double the doses, repeated twice with a 10-day interval. The QuEChERS method underwent validation for linearity, matrix match, accuracy, and precision in bell pepper matrices for residue analysis. The limit of detection for the tested pesticides on bell peppers was 0.01 mg/L, with a quantification limit of 0.05 mg/L. Recovery studies showed a range of 94.80% to 102.80%. Initial deposits of deltamethrin, ethion, fenazaquin, and fenpropathrin on bell peppers at recommended doses were 0.371, 1.237, 0.617, and 0.640 mg/L, respectively, and at double doses were 0.712, 1.945, 1.221, and 1.189 mg/L, respectively. Safe waiting periods of 10, 11, 10, and 8 days were suggested for deltamethrin, ethion, fenazaquin, and fenpropathrin, respectively. The corresponding half-lives for the pesticides were 1.96, 1.79, 2.06, and 1.69 days, all following first-order dissipation kinetics. Dietary risk assessment indicated Hazard Quotients (HQ) below 1 and Theoretical Maximum Daily Intake (TMDI) below Acceptable Daily Intake (ADI) and Maximum Permissible Intake (MPI) levels. Therefore, at their recommended doses, the pesticides were deemed safe for bell pepper cultivation.

Exploring sources of inaccuracy and irreproducibility in the CDC bottle bioassay through direct insecticide quantification.

BACKGROUND: The Centers for Disease Control and Prevention (CDC) bottle bioassay is a commonly used susceptibility test for measuring insect response to insecticide exposure. However, inconsistencies and high variability in insect response when conducting CDC bottle bioassays have been reported in previous publications. We hypothesized that the CDC bottle bioassay results may be compromised when expected and actual insecticide concentrations in the bottles are not equivalent and that inadequate bottle cleaning and/or loss during insecticide introduction and bottle storage steps could be responsible. We explored this hypothesis by quantifying insecticides using gas chromatography tandem mass spectrometry (GC-MS/MS) in bottles that had been cleaned, prepared, and stored according to the CDC guidelines. METHODS: We investigated the bottle cleaning, preparation, and storage methods outlined in the CDC bottle bioassay procedure to identify sources of irreproducibility. We also investigated the effectiveness of cleaning bottles by autoclaving because this method is commonly used in insecticide assessment laboratories. The two insecticides used in this study were chlorpyrifos and lambda-cyhalothrin (λ-cyhalothrin). Insecticides were removed from glass bioassay bottles by rinsing with ethyl-acetate and n-hexane and then quantified using GC-MS/MS. RESULTS: The CDC bottle bioassay cleaning methods did not sufficiently remove both insecticides from the glass bottles. The cleaning methods removed chlorpyrifos, which has higher water solubility, more effectively than λ-cyhalothrin. Chlorpyrifos experienced significant loss during the bottle-coating process whereas λ-cyhalothrin did not. As for bottle storage, no significant decreases in insecticide concentrations were observed for 6 h following the initial drying period for either insecticide. CONCLUSIONS: The CDC bottle bioassay protocol is susceptible to producing inaccurate results since its recommended bottle cleaning method is not sufficient and semi-volatile insecticides can volatilize from the bottle during the coating process. This can lead to the CDC bottle bioassay producing erroneous LC50 values. High levels of random variation were also observed in our experiments, as others have previously reported. We have outlined several steps that CDC bottle bioassay users could consider that would lead to improved accuracy and reproducibility when acquiring toxicity data.

Pesticides in water and sediments from natural protected areas of Spain and their associated ecological risk.

In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices.

Dual-functional metal-organic framework for chemisorption and colorimetric monitoring of cyanogen chloride.

Given the growing concern over the deployment of toxic chemicals in warfare, the rapid and accurate removal and detection of cyanogen chloride (CK) as a blood agent has become increasingly critical. However, conventional physisorbents and chemisorbents used in military respirators are insufficient for the effective removal of CK. In this study, we demonstrate the chemisorption and sensing abilities of Co2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) for CK via electrophilic aromatic substitution (EAS) in humid environments. Unlike the chemisorption in triethylenediamine (TEDA) impregnated carbon materials, which generates by-products through hydrolysis, the electron-rich C5 sites in m-DOBDC4- ligands give rise to cyano substitution with CK. This leads to the formation of stable C-C bonds and chloride ions (Cl-) coordinating with open Co2+ sites. Such a mechanism prevents the generation of toxic by-products like cyanic acid and hydrochloric acid. Breakthrough experiments conducted in a packed-bed system conclusively demonstrated the superior CK removal capacity of Co2(m-DOBDC) (1662 min/g), compared to TEDA-impregnated activated carbon (323 min/g) under humid conditions. Considering that MOF-74 series, isostructural with Co2(m-DOBDC), barely adsorb CK under similar conditions, this finding marks a significant advancement in developing novel sorbents for CK removal. Moreover, this chemisorption not only exhibited rapid and highly efficient CK removal but also enabled colorimetric monitoring via the distinctive color change induced by the coordination of Cl- acting as σ donors. These findings facilitate the development of adsorption and sensing equipment to protect military personnel from toxic chemical threats.

The mother-offspring transfer of chlorothalonil through human breast milk: A multi-city cross-sectional study.

4-Hydroxychlorothalonil (4-OH CHT), the main metabolite of chlorothalonil and the most widely used fungicide, has been frequently detected in human samples during monitoring. 4-OH CHT may exhibit higher toxicity and persistence in the environment compared to its prototype. In this study, a total of 540 paired serum and breast milk samples from pregnant women in three provinces in China were monitored for contaminant residues. 4-OH CHT was analyzed in the samples using ultra high-performance liquid chromatography - high-resolution mass spectrometry with a detection limit of 20 ng/L. The study investigated the effects of demographic factors, such as BMI, region of residence, and education level, on the levels of 4-OH CHT residues in serum and breast milk. Among the three provinces, the highest median concentration of 4-OH CHT in serum samples was observed in Hebei (1.04 × 103 ng/L), while the highest median concentration of 4-OH CHT in breast milk samples was observed in Hubei and Guangdong (491 ng/L). Multiple linear regression was used to investigate the significant positive correlation between 4-OH CHT in serum and breast milk (p = 0.000) after adjusting for personal characteristics. Based on this, the study further explored the influencing factors of transfer efficiencies (TEs) in conjunction with the individual TEs and the personal characteristics of the participants. Our results demonstrated that the age of the volunteers and their exercise habits had an effect on TEs, but further studies are needed to determine whether exercise leads to an increase in TEs.

Portable and Flexible Hydrogel Sensor for On-Site Atrazine Assay on Agricultural Products.

There is growing attention focused toward the problems of ecological sustainability and food safety raised from the abuse of herbicides, which underscores the need for the development of a portable and reliable sensor for simple, rapid, and user-friendly on-site analysis of herbicide residues. Herein, a novel multifunctional hydrogel composite is explored to serve as a portable and flexible sensor for the facile and efficient analysis of atrazine (ATZ) residues. The hydrogel electrode is fabricated by doping graphite-phase carbon nitride (g-C3N4) into the aramid nanofiber reinforced poly(vinyl alcohol) hydrogel via a simple solution-casting procedure. Benefiting from the excellent electroactivity and large specific surface area of the solid nanoscale component, the prepared hydrogel sensor is capable of simple, rapid, and sensitive detection of ATZ with a detection limit down to 0.002 ng/mL and per test time less than 1 min. After combination with a smartphone-controlled portable electrochemical analyzer, the flexible sensor exhibited satisfactory analytical performance for the ATZ assay. We further demonstrated the applications of the sensor in the evaluation of the ATZ residues in real water and soil samples as well as the user-friendly on-site point-of-need detection of ATZ residues on various agricultural products. We envision that this flexible and portable sensor will open a new avenue on the development of next-generation analytical tools for herbicide monitoring in the environment and agricultural products.

Determination of chlorothalonil in vegetables/fruits using liquid chromatography-tandem mass spectrometry with a discharge adapter interface.

RATIONALE: Chlorothalonil (CHT), a broad-spectrum fungicide, has been employed widely to control foliar diseases, whereas with a major metabolite of polar 4-hydroxychlorothalonil (CHT-4-OH), only an acceptable nonpolar CHT residue is allowed by most countries. This study involves the method development for CHT residue in vegetables/fruits using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a novel modified discharge-adaptor (DA) interface. METHODS: CHT residue was analyzed using LC-MS/MS with DA interface (LC-DA-MS/MS), developed in our previous works. A DA was placed on the electrospray tip to switch the ionization modes. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied to extract CHT residue of vegetables/fruits efficiently with less sample preparation time and analysis cost. RESULTS: CHT and CHT-4-OH spiked in four different vegetables/fruits were extracted using the modified QuEChERS method. After LC with isocratic elution, CHT and CHT-4-OH were separated within 3 min. Using LC-DA-MS/MS, the ion signals of CHT were improved two to three times, and the limit of quantification of 5 ng/g and linearity (r2 > 0.99) in the range of 5-200 ng/g were achieved using 10 g of vegetables/fruits. The precision and accuracy were within 15% each. The modified QuEChERS and LC-DA-MS/MS were applied to examine eight field-grown vegetables/fruits; 9.5 and 2588.9 ng/g of CHT were detected in two vegetables/fruits. CONCLUSION: LC-DA-MS/MS combined with modified QuEChERS was successfully applied to determine CHT residue <10 ng/g in vegetables/fruits and with satisfied validation results. The developed method could reduce both analysis cost and time, attributing to simplifications in modified QuEChERS, isocratic elution, and DA interface in LC-DA-MS/MS.

Quantum-level investigation of air decomposed pollutants gas sensor (Pd-modified g-C3N4) influenced by micro-water content.

In the electrical industry, there are many hazardous gases that pollute the environment and even jeopardize human health, so timely detection and effective control of these hazardous gases is of great significance. In this work, the gas-sensitive properties of Pd-modified g-C3N4 interface for each hazardous gas molecule were investigated from a microscopic viewpoint, taking the hazardous gases (CO, NOx) that may be generated in the power industry as the detection target. Then, the performance of Pd-modifiedg-C3N4 was evaluated for practical applications as a gas sensor material. Novelly, an unconventional means was designed to briefly predict the effect of humidity on the adsorption properties of this sensor material. The final results found that Pd-modified g-C3N4 is most suitable as a potential gas-sensitizing material for NO2 gas sensors, followed by CO. Interestingly, Pd-modified g-C3N4 is less suitable as a potential gas-sensitizing material for NO gas sensors, but has the potential to be used as a NO cleaner (adsorbent). Unconventional simulation explorations of humidity effects show that in practical applications Pd-modified g-C3N4 remains a promising material for gas sensing in specific humidity environments. This work reveals the origin of the excellent properties of Pd-modified g-C3N4 as a gas sensor material and provides new ideas for the detection and treatment of these three hazardous gases.

Unveiling carcinogenic pollutant levels in environmental water samples through facile fabrication of gold nanoparticles on sulfur-doped graphitic carbon nitride.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.

A facile and intelligent detection method for diclazuril based on a stable dual emissive Eu3+-dopped metal-organic framework.

Diclazuril (DIC) is a broad-spectrum anti-coccidiosis drug of the triazine class, widely used in poultry farming. The overuse of DIC may lead to its accumulation in animal bodies, which may enter the food chain and threaten human health. In this work, we fabricated a stable Eu3+-doped UiO-66 fluorescence sensor (EuUHIPA-30) for the sensitive detection of DIC. Among 20 veterinary drugs, the fluorescence of EuUHIPA-30 selectively responds to DIC, with a low detection limit (0.19 µM) and fast response (10 s). EuUHIPA-30 is recyclable and can detect DIC in chicken and eggs with good recoveries. Moreover, a smartphone-integrated paper-based sensor enables the instrument-free, rapid, visual, and intelligent detection of DIC in chickens and eggs. This work provides a promising candidate for practical fluorescent DIC sensing in animal-derived food to promote food safety.

Residues determination, risk assessment, and dissipation behavior of myclobutanil formulation on apple.

This study aimed to investigate the dissipation pattern, risk assessment, and waiting period of myclobutanil on apple fruit (Malus domestica Borkh.) under temperate conditions in Kashmir, India. The study involved the application of myclobutanil 10 WP at a single recommended dosage (125 g a.i. ha-1) and double dosage (250 g a.i. ha-1) on Red Velox apple trees, 2 months before harvest. GC equipped with an electron capture detector was used to analyze myclobutanil residues in fruit samples. The study revealed that myclobutanil, at both recommended and double recommended doses, dissipated rapidly and became nondetectable after 55 and 60 days, respectively. The waiting period for myclobutanil application was determined to be 12.41 days for the single dose and 25.58 days for the double dose, respectively. These waiting periods were based on the maximum residue limit of 0.6 ppm as prescribed by the Codex Alimentarius Commission, Food Safety and Standards Authority of India, and European Commission. The study concludes that myclobutanil 10 WP is safe for consumers at both recommended and double recommended doses when applied 2 months before harvest. Risk assessment, considering the average daily apple consumption in India and theoretical maximum residue contributions (TMRCs), indicates negligible health hazards even at double the recommended dosage. The calculated TMRC values at Day 0 were significantly below the maximum permissible intake. For average and maximum myclobutanil residues at single and double doses, the TMRC values were found to be 0.0069 and 0.0070 mg day-1 person-1 and 0.0105 and 0.0106 mg day-1 person-1, respectively. These results indicate that myclobutanil, when used according to recommended dosages and waiting periods, poses minimal health risks to consumers. The study emphasizes the importance of prudent fungicide use to minimize fungicide residues on fruits, thereby ensuring their safety for consumption.

Pesticides residues in leafy green vegetables and irrigation waters in Accra, Ghana.

Pesticides are used in vegetable farming to control pests and diseases, reduce crop losses and improve yield. The study examined pesticide residues in irrigation waters and leafy green vegetables grown in some farming areas in Accra, Ghana. Three types of irrigation water sources (n = 23) and two exotic and four indigenous Ghanaian leafy vegetables (n = 34) from 10 farming areas in Accra, Ghana were collected and examined for 15 organochlorines, 13 organophosphorus and 9 synthetic pyrethroids pesticide residues using the modified QuEChERS procedure. Pesticide residues were detected on 50% (17/34) of the leafy vegetable and 52% (12/23) of the irrigation water samples analysed. Chlorpyrifos and deltamethrin were the most detected pesticide residues in the vegetables and irrigation water. About 26.5% of the vegetables contained pesticide residues exceeding the EU maximum residue limits, so vegetable farmers should be encouraged to comply with appropriate measures on pesticide use to enhance food safety.

Identification and characterization of cytochrome P450 CYP77A59 of loquat (Rhaphiolepis bibas) responsible for biosynthesis of phenylacetonitrile, a floral nitrile compound.

MAIN CONCLUSION: Cytochrome P450 CYP77A59 is responsible for the biosynthesis of phenylacetonitrile in loquat flowers. Flowers of some plants emit volatile nitrile compounds, but the biosynthesis of these compounds is unclear. Loquat (Rhaphiolepis bibas) flowers emit characteristic N-containing volatiles, such as phenylacetonitrile (PAN), (E/Z)-phenylacetaldoxime (PAOx), and (2-nitroethyl)benzene (NEB). These volatiles likely play a defense role against pathogens and insects. PAN and NEB are commonly biosynthesized from L-phenylalanine via (E/Z)-PAOx. Two cytochrome P450s-CYP79D80 and "promiscuous fatty acid ω-hydroxylase" CYP94A90, which catalyze the formation of (E/Z)-PAOx from L-phenylalanine and NEB from (E/Z)-PAOx, respectively-are involved in NEB biosynthesis. However, the enzymes catalyzing the formation of PAN from (E/Z)-PAOx in loquat have not been identified. In this study, we aimed to identify candidate cytochrome P450s catalyzing PAN formation in loquat flowers. Yeast whole-cell biocatalyst assays showed that among nine candidate cytochrome P450s, CYP77A58 and CYP77A59 produced PAN from (E/Z)-PAOx. CYP77As catalyzed the dehydration of aldoximes, which is atypical of cytochrome P450; the reaction was NADPH-dependent, with an optimum temperature and pH of 40 °C and 8.0, respectively. CYP77As acted on (E/Z)-PAOx, (E/Z)-4-hydroxyphenylacetaldoxime, and (E/Z)-indole-3-acetaldoxime. Previously characterized CYP77As are known to hydroxylate fatty acids; loquat CYP77As did not act on tested fatty acids. We observed higher expression of CYP77A59 in flowers than in buds; expression of CYP77A58 was remarkably reduced in the flowers. Because the flowers, but not buds, emit PAN, CYP77A59 is likely responsible for the biosynthesis of PAN in loquat flowers. This study will help us understand the biosynthesis of floral nitrile compounds.

Determination of acaricides in honeys from different botanical origins by gas chromatography-mass spectrometry.

An analytical method has been proposed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in honeys from different botanical origins (multifloral, heather and rosemary) by means of gas chromatography-mass spectrometry. An efficient and simple sample treatment was proposed that involved a solvent extraction with an ethyl acetate and cyclohexane (50:50, v/v) mixture. Chromatographic analysis (<25 min) was performed in a DB-5MS column under programmed temperature conditions. The method was validated in terms of selectivity, limits of detection (0.2-2.0 µg kg-1) and quantification (0.5-7.6 µg kg-1), linearity (limit of quantification-700 (heather) or 800 (multifloral and rosemary) µg kg-1), matrix effect (<20 % in most cases), trueness (recoveries between 81 % and 108 %), and precision (relative standard deviation < 15 %). Finally, of the seven acaricides investigated in several honey samples only τ-fluvalinate residues (

Role of Sulfur Compounds in Vegetable and Mushroom Aroma.

At the base of the food pyramid is vegetables, which should be consumed most often of all food products, especially in raw and unprocessed form. Vegetables and mushrooms are rich sources of bioactive compounds that can fulfill various functions in plants, starting from protection against herbivores and being natural insecticides to pro-health functions in human nutrition. Many of these compounds contain sulfur in their structure. From the point of view of food producers, it is extremely important to know that some of them have flavor properties. Volatile sulfur compounds are often potent odorants, and in many vegetables, belonging mainly to Brassicaeae and Allium (Amaryllidaceae), sulfur compounds determine their specific flavor. Interestingly, some of the pathways that form volatile sulfur compounds in vegetables are also found in selected edible mushrooms. The most important odor-active organosulfur compounds can be divided into isothiocyanates, nitriles, epithionitriles, thiols, sulfides, and polysulfides, as well as others, such as sulfur containing carbonyl compounds and esters, R-L-cysteine sulfoxides, and finally heterocyclic sulfur compounds found in shiitake mushrooms or truffles. This review paper summarizes their precursors and biosynthesis, as well as their sensory properties and changes in selected technological processes.

Effects of combined treatment of plasma activated liquid and ultrasound for degradation of chlorothalonil fungicide residues in tomato.

The effects of combined treatment (PAL-U) of plasma-activated liquid (PAL) including plasma-activated water (PAW) and plasma-activated buffer solution (PABS) and ultrasound (U) for the degradation of chlorothalonil fungicide on tomato fruit was investigated. Distilled water and buffer solution were activated by radiofrequency plasma jet for durations of 1, 3, 5, and 10 min to obtain PAL1 to PAL10. Fruits were immersed in PAL for 15 min and also in distilled water with sonication for 15 min for individual treatments, and in PAL with sonication for 15 min for combined treatments. The maximum chlorothalonil fungicide residues were reduced by 89.28 and 80.23% for PAW10-U and PABS10-U, respectively. HPLC-MS characterization revealed chlorothalonil degradation pathway and formation of 2,4,5-trichloroisophthalonitrile, 2,4-dichloroisophthalonitrile, 4-chloroisophthalonitrile, isophthalonitrile and phenylacetonitrile as degradation products. Treatments also showed no negative effects on tomato quality. Therefore, PAL and PAL-U treatments could serve as effective methods for degrading pesticides on tomatoes.

Cyanogenesis in cassava and its molecular manipulation for crop improvement.

While cassava is one of the most important staple crops worldwide, it has received the least investment per capita consumption of any of the major global crops. This is in part due to cassava being a crop of subsistence farmers that is grown in countries with limited resources for crop improvement. While its starchy roots are rich in calories, they are poor in protein and other essential nutrients. In addition, they contain potentially toxic levels of cyanogenic glycosides which must be reduced to safe levels before consumption. Furthermore, cyanogens compromise the shelf life of harvested roots due to cyanide-induced inhibition of mitochondrial respiration, and associated production of reactive oxygen species that accelerate root deterioration. Over the past two decades, the genetic, biochemical, and developmental factors that control cyanogen synthesis, transport, storage, and turnover have largely been elucidated. It is now apparent that cyanogens contribute substantially to whole-plant nitrogen metabolism and protein synthesis in roots. The essential role of cyanogens in root nitrogen metabolism, however, has confounded efforts to create acyanogenic varieties. This review proposes alternative molecular approaches that integrate accelerated cyanogen turnover with nitrogen reassimilation into root protein that may offer a solution to creating a safer, more nutritious cassava crop.

A colorimetric test for the evaluation of the insecticide content of LLINs used on Bioko Island, Equatorial Guinea.

BACKGROUND: Insecticide-treated nets and indoor residual spraying of insecticides are used as the vector control interventions in the fight against malaria. Measuring the actual amount of deposits of insecticides on bed nets and walls is essential for evaluating the quality and effectiveness of the intervention. A colorimetric "Test Kit" designed for use as a screening tool, able to detect the type II pyrethroids on fabrics and sprayed walls, was used for the first time to detect deltamethrin on long-lasting insecticidal nets (LLINs) deployed on Bioko Island, Equatorial Guinea. METHODS: LLINs were analysed using the colorimetric Test Kit performed in situ, which leads to the formation of an orange-red solution whose depth of colour indicates the amount of type II pyrethroid on the net. The kit results were validated by measuring the amount of extracted insecticide using high-performance liquid chromatography (HPLC) with diode array detection (DAD). RESULTS: Deltamethrin concentration was determined for 130 LLINs by HPLC-DAD. The deltamethrin concentration of these nets exhibited a significant decrease with the age of the net from 65 mg/m2 (< 12 months of use) to 31 mg/m2 (> 48 months; p < 0.001). Overall, 18% of the nets being used in households had < 15 mg/m2 of deltamethrin, thus falling into the "Fail" category as assessed by the colorimetric Test Kit. This was supported by determining the bio-efficacy of the nets using the WHO recommended cone bioassays. The Test Kit was field evaluated in situ and found to be rapid, accurate, and easy to use by people without laboratory training. The Test Kit was shown to have a reliable linear relationship between the depth of colour produced and deltamethrin concentration (R2 = 0.9135). CONCLUSION: This study shows that this colorimetric test was a reliable method to assess the insecticidal content of LLINs under operational conditions. The Test Kit provides immediate results and offers a rapid, inexpensive, field-friendly alternative to the complicated and costly methods such as HPLC and WHO cone bioassays which also need specialist staff. Thus, enabling National Malaria Control Programmes to gain access to effective and affordable monitoring tools for use in situ.