Simultaneous Quantification of Two Neonicotinoids Using QuEChERS-LC-MS/MS in Moroccan Spearmint (Mentha Spicata.L): Qualimetry of the Method by Uncertainty Estimation Using Generalized Pivotal Quantities Approach and Monte Carlo Simulation.

BACKGROUND: Neonicotinoids (NEOs) are used for the phytosanitary treatment of Mentha Spicata.L crops, and this practice requires precise control of these harmful substances at very low concentrations. OBJECTIVE: The objective of this study is to apply an approach allowing simultaneously validation and evaluation of measurement uncertainty based on total error methodology, in order to accurately quantify the presence of two NEOs in Mentha Spicata.L utilizing a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS)-LC-MS/MS methodology. METHODS:  The quantification of imidacloprid and acetamiprid employing a QuEChERS extraction method, coupled with LC-MS/MS, ensuring the accuracy of the analytical method and managing the risks associated with its routine use. A complete and exhaustive validation approach based on the "ß-content, γ-confidence" tolerance interval was used for the uncertainty assessment, using the generalized pivot quantity (GPQ) concept and Monte Carlo simulation, which avoids the need for additional data while achieving intermediate precision for each concentration level within predetermined acceptable limits. RESULTS: The validation procedure is based on the choice of a quadratic model for the two NEOs, allowing the validation of acetamiprid and imidacloprid by LC-MS/MS assay within the range of working concentration. The flexibility of the uncertainty profile intervals was demonstrated with a variation in ß-content values (66.7, 80, and 90%) and risk values (10 and 5%), which remained within the acceptability limits of 20%, and the relative expanded uncertainty did not exceed 15 and 11%. CONCLUSION: A QuEChERS-LC-MS/MS method for the analysis of two NEOs has been successfully fully validated using the uncertainty profile strategy. HIGHLIGHTS: Implementation of an overall validation strategy, which involves both the validation and uncertainty assessment known as the uncertainty profile, for the quantification of two important NEOs in Mentha Spicata.L using QuEChERS-LC-MS/MS. This qualimetric approach has been conducted by computing the measurement uncertainty of the method utilizing data from analytical validation under conditions of intermediate precision at each level of concentration without additional effort. After that we have demonstrated the flexibility of this strategy for the LC-MS/MS quantification of acetamiprid and imidacloprid, using a decision tool that enables the choice and modification of ß-content and γ-confidence values.

An Overall Validation Approach Based on ß-Content, γ-Confidence Tolerance Interval, and Uncertainty Profile: Application to LC-MS/MS Quantification of Carbendazim in Drinking Water.

BACKGROUND: Carbendazim is a fungicide which can seep into the water supply, presenting a public health risk, and therefore the accurate trace determination of this substance is very important. OBJECTIVE: The purpose of the study is to take a top-down analytical validation approach in order to determine the amount of carbendazim in drinking water by using an SPE-LC-MS/MS technique. METHODS: Quantification of carbendazim using solid-phase extraction coupled with LC-MS/MS was used in order to ensure the accuracy of the analytical method and to control the risk of its routine application. An overall validation methodology based on two-sided tolerance interval type ß-content, γ-confidence has been applied for the validation and estimation of uncertainty by building a decision graphical tool called the "uncertainty profile" by using the statistical process known as the Satterthwaite approximation with no recourse to additional data by satisfying intermediate precision condition for each concentration level within the acceptance limits fixed in advance. RESULTS: The process of validation is based on the selection of a linear weighted 1/X model enabling validation of the carbendazim dosage using LC-MS/MS in the range of working concentrations as the ßγ-CCTI fell inside acceptable limits of ±10%, and the relative expanded uncertainty did not surpass 7% regardless of the ß values (66.7, 80, and 90%) and the 1- γ = risk (10 and 5%). CONCLUSION: The application of the uncertainty profile approach for full validation of a SPE-LC-MS/MS assay for the quantification of carbendazim has been successfully achieved. HIGHLIGHTS: Implementation of a full validation strategy based on validation and measurement uncertainty with no additional effort using data from analytical validation under intermediate precision conditions at each level of concentration for carbendazim quantification in drinking water using SPE-LC-MS/MS. So we have shown the flexibility of this approach for carbendazim assay by LC-MS/MS. Indeed, It provides an efficient decision-making tool that allows selection and modification of ß-content and γ-confidence values.

Phytochemical profile, in vivo anti-inflammatory and wound healing activities of the aqueous extract from aerial parts of Cistus ladanifer L.

Cistus ladanifer L. is a Mediterranean shrub, well recognized for its many pharmacological properties. The present study aimed to investigate the phytochemical profile, the in vivo anti-inflammatory and the wound healing activities of the aqueous extract from its aerial parts (AECL). The in vivo anti-inflammatory and the wound healing properties were evaluated by carrageenan-induced paw edema (CAECL) and burn wound in rats, respectively. The results showed that six compounds belonging to flavonoids and tannins were identified in the AECL extract. Moreover, the AECL administrated orally at a dose of 500 mg/kg significantly reduced edema with a percentage of 72 % in terms of inflammation inhibition, using indomethacin as reference drug. On the other hand, when administrated topically, both doses of CAECL cream (5 % and 10 %) manifested a significant anti-inflammatory action using diclofenac as reference drug with a percentage reduction of inflammation that reached 85 % (CAECL-10). As far as wound healing is concerned, the CAECL showed higher effect at a dose of 10 % (CAECL-10) producing a wound contraction of 96 %, similar to that of the reference drug. The findings of the present study indicate that the aqueous extract from aerial parts of Cistus ladanifer L. display strongly anti-inflammatory and wound healing effects to be advantageously used for medical purposes.