Pyrimethanil Research Articles

High resistance levels to pyrimethanil and fludioxonil among fourteen Penicillium spp. from pome fruits in the U.S. Pacific Northwest

In this study, 162 Penicillium isolates, i.e., 31 P. expansum isolates and 131 isolates from 13 other Penicillium spp. referred to as “non-expansum” were collected from apples and pears from multiple packinghouses in Washington State and Oregon. The sensitivity of the isolates to the postharvest fungicides pyrimethanil (PYR) and fludioxonil (FDL) was assessed in vitro. The mean EC50 value for PYR was 0.75 μg/mL in P. expansum compared to 1.63, 3.47, 6.95, 7.06 and 32.21 μg/mL in P. solitum, P. palitans, P. commune, P. roqueforti and P. carneum, respectively. For FDL, the mean EC50 value was 0.04 μg/mL in P. expansum compared to >0.80, 1.00, 10.40, 13.99, and 158.10 μg/mL in P. commune, P. palitans, P. roqueforti, P. solitum, and P. paneum, respectively. Overall, > 40 % of isolates from five “non-expansum” species showed dual resistance to PYR and FDL versus 9.6 % in P. expansum. The recommended rates of PYR and FDL failed to control isolates of six Penicillium spp. on detached apples after five months at 1.5 °C. Sequencing of the Mdl1, NikA, and Os1 genes from different isolates of eight species revealed a high polymorphism in the Mdl1 and NikA of several “non-expansum” species. Three and two concurrent mutations, in addition to a G409R and S959, were detected in the Mdl1 and NikA, respectively, that potentially confer resistance to PYR and FDL. The high level of resistance and the control failure observed on fruits highlight the potential risk posed by several “non-expansum” Penicillium species to pome fruit packers.

Synergistic antifungal effect and potential mechanism of Dimethomorph combined with Pyrimethanil against Phytophthora capsici

Synergistic effect of dimethomorph (DIM) and pyrimethanil (PYM) was evaluated using the Wadley method and the molecular mechanism of the antifungal effects of the combined treatment was systematically investigated. DIM+PYM had a synergistic effect on Phytophthora capsici, with the synergistic effect being observed at 5:1, at which the synergy coefficient was 1.8536. The mycelia of the pathogen treated with DIM+PYM were branched, uneven in thickness, and swollen. Moreover, scanning electron microscopy (SEM) revealed that DIM+PYM caused mycelium breaks, swelling, and apex enlargement, while transmission electron microscopy (TEM) revealed structural damage, cavities, and cell membrane morphological abnormalities. DIM+PYM inhibited the growth of mycelia, destroyed the cell membrane, interfered with energy metabolism, reduced protein and sugar content. Additionally, the transcriptome and metabolome of fungi treated with DIM+PYM changed significantly; specifically, there were 1571 differentially expressed genes and 802 differential metabolites. DIM+PYM may mainly damage the cell membrane, energy, protein, soluble sugar pathways.

Construction of fungicide nano delivery platform through crystal engineering for sustainable fungal control

The adverse effects resulting from off-target pesticide application pose significant risks to both ecosystems and public health. Therefore, developing a pesticide delivery system that is straightforward, effective, and devoid of secondary pollution is crucial for environmental safety. Herein, self-assembled crystalline materials involved pyrimethanil (PYR) and organic acids were constructed by crystal engineering. These materials allowed for direct manipulation of the physicochemical properties and environmental fate of PYR by the building modules. The melting point of PYR was increased from 96.19 °C to 206.69 °C. The photostability and volatile stability were improved by 3.85-fold and 297-fold, respectively. Afterwards, these crystalline materials were prepared as nano cocrystal suspensions (NCSs) in water by the one-pot method. The PYR NCSs exhibited potent bioactivity against Botrytis cinerea and demonstrated slow-release behavior. Upon foliar spraying, the PYR NCSs exhibited desirable foliar wettability with a contact angle lower than 36°. By limiting leaching into the soil and reducing environmental pesticide exposure, PYR NCS ensured the safety of both earthworms and plants. The structure–property relationships of PYR NCSs were elucidated through intermolecular interaction analysis and theoretical calculations. Overall, the NCSs constructed by the supramolecular chemistry strategy are characterized by the simple preparation, high bioactivity, stability, no carrier, slow-release, and minimal environmental risk, which offers insight for improving the utilization and sustainable management of pesticides.

Quantitative MALDI-MS and Imaging of Fungicide Pyrimethanil in Strawberries with 2-Nitrophloroglucinol as an Effective Matrix.

This work explores the use of 2-nitrophloroglucinol (2-NPG) as a matrix for quantitative analysis of the fungicide Pyrimethanil (PYM) in strawberries using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) and imaging. 2-NPG was selected for PYM analysis for optimum sensitivity and precision compared to common matrices α-cyano-4-hydroxylcinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB). PYM-sprayed strawberries were frozen 0, 1, 3, and 4 days after treatment and sectioned for MALDI imaging. The remaining part of each strawberry was processed using quick easy cheap effective rugged and safe (QuEChERS) extraction and analyzed by MALDI-MS and ultraperformance liquid chromatography multireaction-monitoring (UPLC-MRM). MALDI-MS showed comparable performance to UPLC-MRM in calibration, LOD/LOQ, matrix effect, and recovery, with the benefit of fast analysis. The MALDI imaging results demonstrated that PYM progressively penetrated the interior of the strawberry over time and the PYM concentration on tissue measured by MALDI imaging correlated linearly with MALDI-MS and UPLC-MRM measurements and accounts for 79% MALDI-MS and 85% UPLC-MRM values on average. Additionally, quartz crystal microbalance (QCM) was introduced as a new approach to determine strawberry tissue mass per area for MALDI imaging absolute quantitation with sensitive, direct, and localized measurements. This work demonstrates the first example of absolute quantitative MALDI imaging of pesticides in a heterogeneous plant tissue. The novel use of the 2-NPG matrix in quantitative MALDI-MS and imaging could be applied to other analytes, and the new QCM tissue mass per area method is potentially useful for quantitative MALDI imaging of heterogeneous tissues in general.

Novel litchi-like Au–Ag nanospheres driven dual-readout lateral flow immunoassay for sensitive detection of pyrimethanil

Pyrimethanil (PYR) is a fungicide that is harmful to consumers when present in foods at concentrations greater than maximum permitted residue levels. High-performance immunoprobes and dual-readout strategy may be useful for constructing sensitive lateral flow immunoassay (LFIA). Herein, the prepared litchi-like Au–Ag bimetallic nanospheres (LBNPs) exhibited high mass extinction coefficients and fluorescence quenching constants. Benefiting from LBNPs and dual-readout mode, the limits of detection of LBNPs-CM-LFIA and LBNPs-FQ-LFIA for PYR were 0.957 and 0.713 ng mL−1, which were 2.54- and 3.41-fold lower than that of gold nanoparticles-based LFIA, respectively. The limits of quantitation of LBNPs-CM-LFIA and LBNPs-FQ-LFIA were 3.740 and 1.672 ng mL−1, respectively. LBNPs-LFIA was applied to detect PYR in cucumber and grape samples with satisfactory recovery (90%–111%). LBNPs-LFIA showed good agreement with LC-MS/MS for the detection of PYR in the samples. Accordingly, this sensitive and accurate dual-readout LFIA based on LBNPs can be effectively applied for food safety.

Potential Antifungal Effect of Copper Oxide Nanoparticles Combined with Fungicides against Botrytis cinerea and Fusarium oxysporum.

Copper oxide nanoparticles (NCuO) have emerged as an alternative to pesticides due to their antifungal effect against various phytopathogens. Combining them with fungicides represents an advantageous strategy for reducing the necessary amount of both agents to inhibit fungal growth, simultaneously reducing their environmental release. This study aimed to evaluate the antifungal activity of NCuO combined with three fungicide models separately: Iprodione (IPR), Tebuconazole (TEB), and Pyrimethanil (PYR) against two phytopathogenic fungi: Botrytis cinerea and Fusarium oxysporum. The fractional inhibitory concentration (FIC) was calculated as a synergism indicator (FIC ≤ 0.5). The NCuO interacted synergistically with TEB against both fungi and with IPR only against B. cinerea. The interaction with PYR was additive against both fungi (FIC > 0.5). The B. cinerea biomass was inhibited by 80.9% and 93% using 20 mg L-1 NCuO + 1.56 mg L-1 TEB, and 40 mg L-1 NCuO + 12 µg L-1 IPR, respectively, without significant differences compared to the inhibition provoked by 160 mg L-1 NCuO. Additionally, the protein leakage and nucleic acid release were also evaluated as mechanisms associated with the synergistic effect. The results obtained in this study revealed that combining nanoparticles with fungicides can be an adequate strategy to significantly reduce the release of metals and agrochemicals into the environment after being used as antifungals.

Zn-coordination polymers for fluorescence sensing various contaminants in water

Luminescent coordination polymers (LCPs) have garnered significant attention from researchers as promising materials for detecting contaminants. In this paper, three new LCPs ([Zn(tib)(opda)]n⋅H2O (1), [Zn3(tib)2(mpda)3]n⋅5H2O (2), [Zn (tib)(ppda)]n⋅H2O (3)) with different structures (LCP 1–3: 1D, 2D, 1D) using phenylenediacetic acid isomers and 1,3,5-tris (1-imidazolyl) benzene (tib) are synthesized. The specific surface areas (BET) of LCP 1–3 are 4 m2/g, 19 m2/g, and 13 m2/g respectively. LCP 1–3 exhibit excellent fluorescence properties and can serve as fluorescent probe for the detection of inorganic contaminants and organic contaminants. Due to the large BET of LCP 2, the detection limits for trace analytes surpass those of LCP 1 and 3. The detection limits of LCP 2 for Fe3+, nitrobenzene (NB), chloramphenicol (CAP), and pyrimethanil (PTH) are 8.3 nM, 0.016 μM, 0.19 μM, and 0.032 μM, respectively, and the fluorescence quenching rates are 98.6 %, 98.8 %, 92.3 %, and 98.8 %, respectively. These values outperform most reported in the literature. The quantum yields of LCP 1–3 are 11.84 %, 25.22 %, 22.00 % respectively. Real sample testing of LCP 1–3 reveals favorable performance, where spiked recoveries of LCP 2 for the detection of pyrimethanil in grape skins ranged from 99.62 % to 119.3 % with a relative standard deviation (RSD) of 0.627 % to 4.56 % (n = 3). The fluorescence quenching mechanism was attributed to a combination of photoelectron transfer (PET), resonance energy transfer (RET), and competitive absorption (CA). This study advances the application of LCPs in luminescence sensing and contributes to the expansion of novel materials for detecting environmental pollutants.

A highly sensitive and selective Cd-MOF fluorescent probe for the detection of His, NB, TC and PTH and its applications in real samples

A novel metal–organic framework (MOF) with the formula of [Cd(CIA)(4,4′-BB)·H2O]·H2O (Cd-MOF) (H2CIA = 5-methoxyisophthalic acid, 4,4′-BB: 4,4′-bis((1H-imidazol-1-yl)methyl)-1,1′-biphenyl) has been designed and synthesized through solvothermal reaction. The structure was characterized by TG, IR, PXRD, elemental analysis, single-crystal X-ray diffraction and XPS. The coordination pattern of the fully deprotonated ligand (CIA) in Cd-MOF is μ2-к1: к0: к2. The complex is found to be a three-dimensional reticular material with good thermal stability. Further study revealed that Cd-MOF has good fluorescence performance and can be used as a fluorescent probe for sensitive detection of histidine (His), nitrobenzene (NB), tetracycline (TC) and pyrimethanil (PTH) in water. Four cycles experiments can be achieved with a low detection limit. The detection limits were 0.3 µM (His), 0.05 µM (NB), 0.2 µM (TC) and 0.01 µM (PTH), respectively. To verify the feasibility of detecting PTH in real samples, we further explored it in water samples and apple peels. The spiked recoveries were 95.3–99.4 % and 97.2–101.2 %, respectively. Finally, the fluorescence quenching mechanism of Cd-MOF in His, NB, TC and PTH detection is discussed in detail.

Self-Assembled Nanoparticles of a Prodrug Conjugate Based on Pyrimethanil for Efficient Plant Disease Management.

Self-assembled nanotechnology is a promising strategy for improving the effective utilization of pesticides due to its distinct advantages. Herein, an amide-bonded prodrug conjugate based on pyrimethanil (PYR) and butyric acid (BA) was successfully synthesized by the nucleophilic substitution reaction and subsequently self-assembled into spherical nanoparticles (PB NPs) with an average size of 85 nm through the solvent exchange method without using any toxic adjuvant. The results showed that PB NPs based on PYR and BA had a synergistic antimicrobial activity against S. sclerotiorum on plant leaves due to good photostability, low volatilization, good surface activity, and improved retention. Additionally, PB NPs could be used by plant cells as nutrients to promote the growth of plants and thus reduced the toxicity of PYR to plant. Therefore, this prodrug conjugate self-assembly nanotechnology would provide a promising strategy for improving the effective utilization rates of pesticides and reducing their toxicities to plants.

Fabrication and Characterization of Antifungal Hydroxypropyl-β-Cyclodextrin/Pyrimethanil Inclusion Compound Nanofibers Based on Electrospinning.

Pyrimethanil (PMT) is an anilinopyrimidine bactericide with poor water solubility, which limits its applications. To improve the physical and chemical properties of PMT, hydroxypropyl-β-cyclodextrin/pyrimethanil inclusion compound nanofibers (HPβCD/PMT-IC-NFs) were fabricated via electrospinning. A variety of analytical techniques were used to confirm the formation of the inclusion compound. Scanning electron microscopy image displayed that HPβCD/PMT-IC-NF was homogeneous without particles. Thermogravimetric analysis indicated that the formation of the inclusion compound improved the thermostability of PMT. In addition, the phase solubility test illustrated that the inclusion compound formed by PMT and HPβCD had a stronger water solubility. The antifungal effect test exhibited that HPβCD/PMT-IC-NF had better antifungal properties. The release experiment confirmed that HPβCD/PMT-IC-NF had a sustained-release effect, and the release curve conformed to the first-order kinetic model equation. In short, the fabrication HPβCD/PMT-IC-NF inhibited improved solubility and thermostability of PMT, thus promoting the development of pesticide dosage form to water-based and low-pollution direction.

Eu3+-postdoped MOFs are used for fluorescence sensing of TNP, TC and pesticides and for anti-counterfeiting ink application

Two europium-postdoped metal organic frameworks (MOFs) Eu3+@1 and Eu3+@2 [1:{[Zn2(bta)(bpy)(H2O)2]·2H2O}n, 2:{[Ni(bta)(bpy)(H2O)2][Ni(bpy)·(H2O)4]·4H2O}n (H4bta = 1, 2, 3, 5-benzenetetracarboxylic acid, bpy = 4, 4′-dipyridine)] were prepared by hydrothermal synthesis and post-synthesis modification. MOFs 1–2 are all three-dimensional network structure connected by (bta)4- and bpy ligands. Eu3+@1 and Eu3+@2 in aqueous solution can achieve the quantitative detection of 2, 4, 6-trinitrobenzene (TNP), tetracycline (TC) and pesticides with high sensitivity and selectivity. In particular, when the volume of TNP increases to 50 μL, the luminescence quenching rate of Eu3+@2 can reach 99.7% and the LOD for TNP can reach 78 nM. Interestingly, Eu3+@1 has a good response to PTH (Pyrimethanil), while Eu3+@2 has a good selectivity to FLU (Fluazinam), and both can be used for rapid in-situ imaging detection of simulated pesticide residues on fresh vegetables. Under UV lamp, Eu3+@1 showed a significant fluorescence quenching effect on PTH in beans, while the fluorescence quenching effect of Eu3+@2 on FLU on cabbage was obvious. Surprisingly, two kinds of composite materials can be used as anti-counterfeiting ink functional material with strong anti-counterfeiting ability and long term stability.

Oxidative Treatments of Pesticides in Rainwater Runoff by HOCl, O3, and O3/H2O2: Effects of pH, Humic Acids and Inorganic Matters

This study systematically investigated the oxidative treatment of five selected pesticides, alachlor (ALA), carbendazim (CAR), diuron (DIU), pyrimethanil (PYR), and tebuconazole (TEB), by comparing their relative reactivities as a function of three different oxidative treatment processes (i.e., chlorine (HOCl), ozone (O3), and ozone/hydrogen peroxide (O3/H2O2)) under various oxidant dosages, reaction times, and pH conditions. For oxidative treatment, pesticide standards were spiked into rainwater. The removal efficiency of the selected pesticides varied considerably depending on the oxidative treatment processes. HOCl, O3, and O3/H2O2 treatments were highly effective at eliminating CAR (>80%) and PYR (>99%), while they were not significantly effective in removing TEB (<20%). In the case of DIU, HOCl (81%) was shown to be more effective than O3 (24%) and O3/H2O2 (49%). The removal efficiency of ALA was in the order of O3/H2O2 (49%) > O3 (20%) > HOCl (8.5%). The effect of increasing the solution pH from 5.0 to 9.0 on pesticide degradation varied between the oxidative treatment processes. Additionally, NH4+, NO2−, and humic acid in rainwater significantly inhibited pesticide degradation.

S-doped TiO2 photocatalyst for visible LED mediated oxone activation: Kinetics and mechanism study for the photocatalytic degradation of pyrimethanil fungicide

The degradation of pyrimethanil (PYR) was investigated through the activation of oxone by the S-TiO2 (ST) photocatalyst under visible LED irradiation. The catalyst characterization revealed that the sulfur doping mechanism was based on the cation (S6+) substitution of Ti4+ in TiO2 lattice. The optimal molar ratio of S/Ti at 0.25 was proven efficient in the PYR degradation. Influences of various reaction parameters including ST loading, oxone dosage, PYR concentration, and initial solution pH were examined. SO4•-, •OH, 1O2, O2•-, and h+ were found to be the reactive species generated in the ST/Oxone/Vis LED process. Different natural water constituents exerted dissimilar effects because of the generation of additional reactive species or their radical scavenging capabilities. Moreover, the reusability test indicates the ST photocatalyst is reusable and stable. A series of degradation intermediates was detected via four major degradation pathways. Overall, the ST/Oxone/Vis LED process was demonstrated to be a promising approach for the removal of organic pollutants.

Pathogenicity and Control of Phacidium lacerum, an Emerging Pome Fruit Pathogen in Washington State.

Phacidium lacerum (anamorph Ceuthospora pinastri) is a recently reported quarantine fungal pathogen responsible for postharvest rot in apples and pears. Very little is known about its pathogenicity, epidemiology, and best management practices. We screened pathogenicity of P. lacerum on twigs from seven and fruit from nine major commercial apple cultivars. Among the nine cultivars tested, detached fruit of Honeycrisp and Gala cultivars were the most susceptible, whereas WA38 (Cosmic Crisp) was the least susceptible (P < 0.05). Effective concentrations to inhibit 50% growth (EC50) were determined in 41 baseline P. lacerum isolates. The mean EC50 values for four postharvest fungicides, i.e., fludioxonil (FDL), difenoconazole (DIF), thiabendazole (TBZ), and pyrimethanil (PYRI) were 0.16, 0.38, 0.54, and 0.72 µg/ml, respectively. The mean EC50 values for four preharvest fungicides, i.e., pyraclostrobin (PYRA), fluxapyroxad (FLUX), boscalid (BOSC), and fluopyram (FLUP) were 0.96, 12.64, 16.54, and 44.46 µg/ml, respectively. In situ efficacy trials were conducted on detached Gala apples treated preventively and curatively with the aforementioned fungicides. After 6 months of storage at 1°C, FDL and DIF provided full control followed by TBZ and PYRI, whereas the other preharvest fungicides provided fair or low efficacies. Findings of this study shed light on pathogenicity of this emerging pathogen and provide necessary knowledge for effective management of Phacidium rot.

A sensitive pyrimethanil sensor based on porous NiCo2S4/graphitized carbon nanofiber film

With the extensive use of pesticides, the problem of pesticide residues has become people's concern. In this work, NiCo2S4 nanoneedle arrays grown on an electrospun graphitized carbon nanofiber film (NiCo2S4/GCNF) is successfully prepared by a simple two-step hydrothermal method, and further applied to detection of fungicide pyrimethanil (PMT). NiCo2S4 arrays exhibit a unique core-shell structure with rough surface, providing abundant electrochemically active sites exposed to the electrolyte. The NiCo2S4/GCNF modified electrode displays excellent electrocatalytic activity, and the electrode surface is controlled both by diffusion and adsorption processes. When applied to PMT determination, NiCo2S4/GCNF sensor displays wide linear range from 0.06 to 800 μM with low detection limit (20 nM). Furthermore, the as-proposed sensor also displays other outstanding advantages, including simple preparation, low cost, perfect reproducibility and good application in practical samples. Such attracting analytical properties could be attributed to high electrocatalytic activity of NiCo2S4 and superior electrical conductivity of GCNF frameworks. In addition, the detailed oxidation mechanism of PMT at NiCo2S4/GCNF electrode was also studied. The results indicate that NiCo2S4/GCNF is a promising platform for PMT sensors.

Residues of anilinopyrimidine fungicides and suspected metabolites in wine samples

The coexistence of the anilinopyrimidine fungicides pyrimethanil (PYR) and cyprodinil (CYP), and suspected metabolites in wine samples was investigated by liquid chromatography (LC) with tandem mass spectrometry (MS/MS), based on triple quadrupole (QqQ) and quadrupole time-of-flight (QTOF) MS instruments. For the first time, quantitative data obtained after solid-phase extraction (SPE) of wine samples have demonstrated the systematic presence of 4-hydroxyanilino derivatives of PYR and CYP in wines containing residues of parent fungicides, at concentrations from 0.2 to 58 ng mL−1. Higher concentration ratios (hydroxylated derivative/active fungicide) were measured in red than in white wines, particularly in case of PYR. On average, the concentrations of PYR-4OH were twice those measured for PYR in red wines. A targeted search of hydroxyl derivatives in wine extracts by LC-QTOF-MS showed the existence of additional hydroxylation positions in the pyrimidine ring and/or in the alkyl substituents bond to this cycle in the structure of both anti-botrytis fungicides. Moreover, free and glycosylated forms of the hydroxylated metabolites for both fungicides coexist in wine samples. In case of CYP, it is proved that hydroxylated and glycosylated metabolites are already present in grapes before vinification.

Flexible and Transparent Substrates Based on Gold Nanoparticles and TiO2 for in Situ Bioanalysis by Surface-Enhanced Raman Spectroscopy.

Flexible and transparent substrates are emerging as low cost and easy-to-operate support for surface-enhanced Raman spectroscopy (SERS). In particular, in situ SERS detection approach for surface characterization in transmission modality can be efficiently employed for non-invasive analysis of non-planar surfaces. Here we propose a new methodology to fabricate a homogenous, transparent, and flexible SERS membrane by the assistance of a thin TiO2 porous layer deposited on the PDMS surface, which supports the uniform loading of gold nanoparticles over large area. The substrate was first characterized for homogeneity, sensitivity and repeatability using a model molecule for SERS, i.e., 7-mercapto-4-methylcoumarin. Satisfactory intra-substrate uniformity and inter-substrates repeatability was achieved, showing an RSD of 10%, and an analytical sensitivity down to 10 nM was determined with an EF of 3.4 × 105 ± 0.4 × 105. Furthermore, SERS detection of pyrimethanil (PMT), a commonly employed pesticide in crops for human consumption, was performed in situ, exploiting the optical transparency of the device, using both model surfaces and non-flat bio-samples. PMT contamination at the phytochemical concentration levels corresponding to commonly used infield doses was successfully detected on the surface of the yellow Ficus benjiamina leaves, supporting the use of this substrate for food safety in-field application.

A Sensitive Pyrimethanil Sensor Based on Electrospun TiC/C Film.

Titanium carbide (TiC) is a very significant transition metal carbide that displays excellent stability and electrical conductivity. The electrocatalytic activity of TiC is similar to noble metals but is much less expensive. Herein, carbon nanofibers (CNFs)-supported TiC nanoparticles (NPs) film (TiC/C) is prepared by electrospinning and carbothermal processes. Well-dispersed TiC NPs are embedded tightly into the CNFs frameworks. The electrochemical oxidation of pyrimethanil (PMT) at the TiC/C-modified electrode displays enhanced redox properties, and the electrode surface is controlled simultaneously both by diffusion and adsorption processes. When TiC/C is applied for PMT determination, the as-fabricated sensor shows good sensing performance, displaying a wide linear range (0.1–600 μM, R2 = 0.998), low detection limit (33 nM, S/N = 3), and good reproducibility with satisfied anti-interference ability. In addition, TiC/C shows long-term stability and good application in natural samples. The facile synthetic method with good sensing performance makes TiC/C promising as novel electrode materials to fabricate efficient sensors.

Biomarkers of Exposure to Pyrimethanil After Controlled Human Experiments.

Pyrimethanil (PYM) is a fungicide used pre- and post-harvest on many crops. It has a low acute toxicity but is of toxicological concern because of its antiandrogenic properties. The aim of the current work was to investigate some metabolism and estimate elimination kinetics of PYM in humans after experimental oral and dermal exposure. A liquid chromatography triple quadrupole mass spectrometry (LC–MS-MS) method was developed and validated for the analysis of PYM and its metabolite 4-hydroxypyrimethanil (OH–PYM) in human urine. The method was applied to analyze urine obtained from two volunteers experimentally exposed to PYM. The elimination of OH–PYM seemed to follow first-order kinetics and a two-phase excretion. After the oral exposure, the elimination half-life of OH–PYM in the rapid phase was 5 and 3 h for the female and male volunteer, respectively. In the slower phase, it was 15 h in both volunteers. After the dermal exposure, the half-life in the rapid phase was 8 h in both volunteers. In the slower phase, it was 30 and 20 h, respectively. About 80% of the oral dose was recovered as urinary OH–PYM in both volunteers. The dermal dose recovered as urinary OH–PYM was 9.4% and 19%, in the female and male volunteer, respectively. OH–PYM was mainly found as a conjugate of sulfonate and glucuronic acid. No free PYM was found. The analytical method showed good within-run, between-run and between-batch precision with a coefficient of variation between 6% and 12%. A limit of detection of 0.1 ng/mL and a limit of quantification of 0.4 ng/mL were achieved for both the analytes. The method was applied to biomonitor PYM exposure in populations in Sweden. OH–PYM was detected in nearly 50% and 96% of samples from the environmentally and occupationally exposed populations, respectively.

Sensitivity of Phacidiopycnis spp. Isolates from Pome Fruit to Six Pre- and Postharvest Fungicides.

Phacidiopycnis washingtonensis and P. pyri cause speck rot and Phacidiopycnis rot on apple and pear, respectively. Infection occurs in the orchard and remains latent, and symptoms appear after months of storage. Decay management relies on orchard sanitation and pre- and postharvest fungicides. In a 2017 survey, speck rot accounted for 6.4% of apple decay in central Washington, whereas Phacidiopycnis rot accounted for 3.9 and 6.7% of total pear decay in Washington and Oregon, respectively. Sensitivities of baseline populations of 110 P. washingtonensis and 76 P. pyri isolates collected between 2003 and 2005 to preharvest fungicides pyraclostrobin (PYRA) and boscalid (BOSC) and to postharvest fungicides thiabendazole (TBZ), fludioxonil (FDL), pyrimethanil (PYRI), and difenoconazole (DFC) were evaluated using a mycelial growth inhibition assay. Mean effective concentrations necessary to inhibit 50% growth (EC50) of P. washingtonensis were 0.1, 0.3, 0.8, 1.8, 2.1, and 4.8 µg/ml for FDL, PYRI, TBZ, DFC, PYRA, and BOSC, respectively. Respective mean EC50 values for P. pyri were 0.2, 0.6, 1.6, 1.1, 0.4, and 1.8 µg/ml. The sensitivity of exposed P. washingtonensis and P. pyri populations collected in 2017 revealed potential shifts toward BOSC and PYRA resistance. The efficacy of the six fungicides to control isolates of each pathogen with different in vitro sensitivity levels was evaluated on apple and pear fruit. FDL, DFC, and PYRI controlled both Phacidiopycnis spp. regardless of their EC50 values after 5 months of storage at 0°C in a regular atmosphere. The consistent occurrence of Phacidiopycnis spp. will require continuous monitoring and development of disease management strategies based on fungicide phenotypes and efficacy of existing fungicides assessed herein.