Dissipation, Residue and Human Dietary Risk Assessment of Pyraclostrobin and Cyazofamid in Grapes Using an HPLC-UV Detector.

Pyraclostrobin is a new broad-spectrum methoxyacrylic acid fungicide. Cyazofamid is a new selective foliar spray acaricide. Here, we studied the degradation rate and final residues of pyraclostrobin and cyazofamid in grape and evaluated their dietary risk to consumers. The average recoveries of pyraclostrobin ether ester, cyazofamid and cyazofamid metabolite (CCIM) in grapes were 84-94%, 92-98% and 99-104%, respectively. The relative standard deviations (RSDs) were 6.0-20.3%, 2.4-10.5% and 1.3-4.0%, respectively, and the LOQs were all 0.05 mg/kg. The digestion dynamics of the experimental sites were in accordance with the first-order kinetic equation. The degradation half-lives of pyraclostrobin ether ester and cyazofamid were 17.8 d-28.9 d and 4.3 d-7.8 d, respectively. The final residues of pyraclostrobin ether ester, cyazofamid and CCIM in grapes were <0.05-1.88 mg/kg, <0.05-0.31 mg/kg and <0.05-0.47 mg/kg, respectively. Using probability models, the total chronic risk values for pyraclostrobin and cyazofamid were calculated to be 0.112-189.617% and 0.021-1.714%, respectively. The results of the contribution analysis indicate that pyraclostrobin poses a much greater risk to Chinese consumers than cyazofamid, especially to children and adolescents, who have a significantly greater risk than adults. This suggests that more consideration should be given to the cumulative risk of compounds for vulnerable groups in the future.

Robust ellipsoidal set-membership fault estimation for time-varying systems with uniform quantization effects over sensor networks.

This article is concerned with the robust set-membership fault estimation problem for a class of uncertain discrete time-varying systems over sensor networks. The system measurements are subject to the uniform quantization which results in the unknown-but-bounded noises. Attention is focused on the design of a set-membership fault estimator such that, in the simultaneous presence of uncertain parameters, unknown-but-bounded noises and uniform quantization effects, the estimation errors are confifined to a certain ellipsoidal region. By using the mathematical induction, a suffificient condition is derived for the existence of the desired fault estimator at each time step in terms of a set of recursive matrix inequalities. Moreover, an optimization problem is formulated by minimizing the ellipsoid of the estimation error. Finally, two numerical examples are provided to illustrate the effectiveness of the proposed fault estimator design scheme.

Targeted and Untargeted Metabolomics Profiling of Wheat Reveals Amino Acids Increase Resistance to Fusarium Head Blight.

Fusarium head blight (FHB), a notorious plant disease caused by Fusarium graminearum (F. graminearum), is severely harmful to wheat production, resulting in a decline in grain quality and yield. In order to develop novel control strategies, metabolomics has been increasingly used to characterize more comprehensive profiles of the mechanisms of underlying plant-pathogen interactions. In this research, untargeted and targeted metabolomics were used to analyze the metabolite differences between two wheat varieties, the resistant genotype Sumai 3 and the susceptible genotype Shannong 20, after F. graminearum inoculation. The untargeted metabolomics results showed that differential amino acid metabolic pathways existed in Sumai 3 and Shannong 20 after F. graminearum infection. Additionally, some of the amino acid contents changed greatly in different cultivars when infected with F. graminearum. Exogenous application of amino acids and F. graminearum inoculation assay showed that proline (Pro) and alanine (Ala) increased wheat resistance to FHB, while cysteine (Cys) aggravated the susceptibility. This study provides an initial insight into the metabolite differences of two wheat cultivars under the stress of F. graminearum. Moreover, the method of optimization metabolite extraction presents an effective and feasible strategy to explore the understanding of the mechanisms involved in the FHB resistance.

Dissipation, Residue, and Dietary Risk Assessment of Bifenthrin, Bifenazate, and Its Metabolite Bifenazate-Diazene in Apples Based on Deterministic and Probabilistic Methods.

A rapid, sensitive, and effective multiresidue analytical method was established to investigate the degradation rate and final residues of bifenthrin, bifenazate, and its metabolite bifenazate-diazene in apples, and the dietary risk of consumers was evaluated. The residues of bifenthrin, bifenazate, and bifenazate-diazene in apple samples from 12 different apple-producing areas of China were determined by high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS). The average recoveries of the three compounds in apples were 88.4-104.6%, and the relative standard deviations (RSDs) were 1.3-10.5%. The limit of quantification (LOQ) for each compound was 0.01 mg/kg. Although the degradation half-lives of bifenthrin, bifenazate, and bifenazate-diazene were 17.8-28.9, 4.3-7.8, and 5.0-5.8 days, under good agricultural practice (GAP) conditions, the final residues of bifenthrin, bifenazate, and the sum of bifenazate and its metabolite bifenazate-diazene in apples were <0.01-0.049, < 0.01-0.027, and <0.02-0.056 mg/kg, respectively, which were lower than the maximum residue limit (MRL) in China. By comparing the deterministic model with the probabilistic model, the results of the probabilistic model at the P95 level (12.91-48.9% for bifenthrin, 17.48-52.01% for bifenazate including its metabolite) were selected as reasonable assessment criteria for chronic dietary risk, and the acute risk was at the P99.9 level (3.00-15.59% for bifenthrin). Although the exposure risk calculated by both the deterministic model and the probabilistic model was less than 100%, the risk to children is significantly higher than that of the general population. This suggests that in future research and policy making, we should pay more attention to the risk of vulnerable groups such as children.

Practical dose delivery verification of craniospinal IMRT.

Craniospinal irradiation (CSI) using IMRT allows dose sparing to organs-at-risk (OAR) whilst conforming the dose to the target volume. Due to the complexity of treatment involving several isocenters, the dose distribution created by the inverse-planned segmented fields must be verified prior to treatment. We propose and test methods to verify dose delivery using commonly available dosimetry equipment for commissioning and routine patient-specific dose verification of craniospinal IMRT. Ten patients treated with conventional CSI were retrospectively planned with a 3-isocenter (cranial, upper spine, and lower spine) IMRT technique. The isocenters were placed 25-27 cm away from each other in the longitudinal direction but in the same lateral and anterioposterior positions. The planning target volume (PTV) was defined as the brain with a 0.5 cm margin and spinal canal with a 1.0 cm margin. The plans were prescribed to 36 Gy in 20 fractions to the PTV mean dose. Eleven beams (five cranial, three upper spine, and three lower spine) were optimized simultaneously. The dose delivered by the IMRT plans was then recalculated on several different phantoms and measured using the following methods: 1) ionization chamber inserted in a cylindrical phantom, positioned in the junction regions between cranial/upper-spine isocenters and upper-/lower-spine isocenters; 2) MapCHECK centered in the overlap regions; and 3) ArcCHECK measurement with beams from each isocenter. For 1) ± 3% dose difference and for 2) and 3) ≥ 95% of measured points with a γ-index < 1 for 3% dose difference and 3 mm distance-to-agreement were deemed clinically acceptable. The median (range) planned to measured dose differences for the ionization chamber is 0.4% (-1.5% to 3.0%) for the cranial/upper-spine field and 1.8% (-0.8% to 2.6%) for the upper-/lower-spine field overlap region. The median (range) percentage of MapCHECK diodes with a γ index < 1 for 3%/3 mm criterion is 98.0% (95.3% to 99.7%) for the cranial/upper-spine and 97.3% (95.0% to 99.6%) for the upper-/lower-spine field overlap regions. The median (range) percentage of ArcCHECK diodes with a γ index < 1 for 3%/3 mm criterion is 99.7% (97.1% to 100%). Three different methods of verifying craniospinal IMRT were compared and tested. All techniques offer different benefits and together can be used for 1) commissioning the treatment technique and, separately, for 2) patient-specific pretreatment verification measurements.

Using maximum entropy model to predict protein secondary structure with single sequence.

Prediction of protein secondary structure is somewhat reminiscent of the efforts by many previous investigators but yet still worthy of revisiting it owing to its importance in protein science. Several studies indicate that the knowledge of protein structural classes can provide useful information towards the determination of protein secondary structure. Particularly, the performance of prediction algorithms developed recently have been improved rapidly by incorporating homologous multiple sequences alignment information. Unfortunately, this kind of information is not available for a significant amount of proteins. In view of this, it is necessary to develop the method based on the query protein sequence alone, the so-called single-sequence method. Here, we propose a novel single-sequence approach which is featured by that various kinds of contextual information are taken into account, and that a maximum entropy model classifier is used as the prediction engine. As a demonstration, cross-validation tests have been performed by the new method on datasets containing proteins from different structural classes, and the results thus obtained are quite promising, indicating that the new method may become an useful tool in protein science or at least play a complementary role to the existing protein secondary structure prediction methods.

An analytic model for the response of a CZT detector in diagnostic energy dispersive x-ray spectroscopy.

A CdZnTe detector (CZTD) can be very useful for measuring diagnostic x-ray spectra. The semiconductor detector does, however, exhibit poor hole transport properties and fluorescence generation upon atomic de-excitations. This article describes an analytic model to characterize these two phenomena that occur when a CZTD is exposed to diagnostic x rays. The analytical detector response functions compare well with those obtained via Monte Carlo calculations. The response functions were applied to 50, 80, and 110 kV x-ray spectra. Two 50 kV spectra were measured; one with no filtration and the other with 1.35 mm Al filtration. The unfiltered spectrum was numerically filtered with 1.35 mm of Al in order to see whether the recovered spectrum resembled the filtered spectrum actually measured. A deviation curve was obtained by subtracting one curve from the other on an energy bin by bin basis. The deviation pattern fluctuated around the zero line when corrections were applied to both spectra. Significant deviations from zero towards the lower energies were observed when the uncorrected spectra were used. Beside visual observations, the exposure obtained using the numerically attenuated unfiltered beam was compared to the exposure calculated with the actual filtered beam. The percent differences were 0.8% when corrections were applied and 25% for no corrections. The model can be used to correct diagnostic x-ray spectra measured with a CdZnTe detector.