MaterialsandMethods
Chemicals and reagents
Cinnamaldehyde (99% purity), cinnamylalcohol (97% purity) and salicylaldehyde (98% purity) were purchased from Sigma‐Aldrich, Saint Louis, USA. The high pressure liquid chromatography (HPLC) grade acetone was obtained from Tedia, Ohio, USA. The ENVI‐Carb solid phase extraction (SPE) cartridge (500 mg, 6 mL), HLB SPE cartridge (60 mg, 3 mL) and Florisil SPE cartridge (1000 mg, 6 mL) were purchased from Supelco, Philadelphia, Waters, Milford, and Applied Separations, Pennsylvania, USA, respectively. Thirteen (11, liquid type and 2, solid type) commercial biopesticides containing cinnamon extract were purchased from eight local companies in Korea.
Selection of marker compounds in biopesticides
Three constituents in the cinnamon extract were selected as marker compounds in the biopesticides: cinnamaldehyde, cinnamylalcohol and salicylaldehyde. GC with flame ionization detector (FID) was used for content analysis.
Method for marker compounds analysis
The marker compounds in biopesticides containing cinnamon extract were analyzed using the ENVI-Carb and HLB SPE cartridges. One mL of diluted biopesticide (100 times) with distilled water (DW) was placed in the ENVI-Carb SPE cartridge and eluted with 12 mL of hexane (3 mL×4). The organic phase was concentrated using an evaporator (Rotavapor R-124) purchased from Büchi, Flawil, Switzerland. Dried residue was then re-dissolved in 2 mL same solvent for GC analysis. The clean up using a HLB SPE cartridge was performed with the modified method of Lee et al. (2013). One mL of diluted biopesticide (20 times) with DW was loaded on the HLB SPE cartridge which was activated with 2 mL of acetone and 1 mL of DW, and eluted with 6 mL (2 mL×3) of acetone after washing with 2 mL of distilled water. Eluate was evaporated and re-dissolved in 5 mL of acetone for the analysis.
Gas chromatography analysis
GC conditions for analyzing cinnamaldehyde, cinnamylalcohol and salicylaldehyde, were: system, Agilent 6890 series with FID (Agilent, Santa Clara, USA); column, RTX‐5 (30 m × 0.25 mm × 0.25 mm, RESTEK, Pennsylvania, USA); carrier gas, He (99.999%, 6 mL min‐1); injector temperature, 230℃; oven temperature, initial 70℃ (2 min hold), 3℃ min‐1, 93℃, 30℃ min‐1, 130℃, 3.5℃ min‐1, 140℃, 40℃ min‐1, 300℃; detector temperature, 300℃; and injection volume, 1 μl.
Method validation
Sample preparation and analytical methods were validated in terms of linearity, limits of quantitation (LOQ), confirmatory and precision. The linearity of the calibration curves was evaluated by standard solution at concentrations 0.05, 0.1, 0.5, 1, 5 and 10 mg L-1, respectively, with five replications. The LOQ for cinnamaldehyde, cinnamylalcohol and salicylaldehyde were the concentration that produced a signal-to-noise ratio of 10. Confirmatory test was done based on the recovery assay results of samples spiked with all analytes at 6 mg L-1, with three replications. Recoveries were calculated by comparing the extracted amounts to the spiked with calibration curves of the cinnamaldehyde, cinnamylalcohol and salicylaldehyde, respectively. The intermediate precision, expressed as relative standard deviation (RSD, %), was determined through the replicates data (five replications) for three days at different levels.
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