This journal is (C) The Royal Society of Chemistry 1 Transmission-Mode Direct Analysis in Real Time and Desorption Electrospray Ionization Mass Spectrometry of Insecticide-Treated Bednets for Malaria Control José J. Pérez 1, Glenn A. Harris 1, Joseph E. Chipuk, Jennifer S. Brodbelt, Michael D. Green 3, Christina Y. Hampton 1, Facundo M. Fernández* 1 1 School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 333 (USA) Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX 771 (USA) 3 Division of Parasitic Diseases, U.S. Centers for Disease Control and Prevention, Atlanta, GA 3341 (USA)
This journal is (C) The Royal Society of Chemistry 1 1 % 4 (a) 5 6,7 1 5 (b) 1 5 1 = [C 7 H 9 Cl ] + = [C 13 H 11 O] + 3 = [C 13 H 11 O ] + 4 = [M + H HCl] + 5 = [M + H H O] + 6 = [M] + 7 = [M + H] + = [M + NH 4 ] + 4 6,7 1 5 15 5 3 35 4 m/z % 1 5 Experimental 1 6 4 1 Theoretical 6 4 44 46 4 41 41 414 416 41 Cl Cl H 3 C CH 3 3 4 6,7 1 15 5 3 35 4 m/z O O O (c) Fig. S1 He-induced DART-TOF MS spectra of a neat permethrin standard obtained at (a) 5 C and (b) 15 C with 1.5 L min -1 gas flow rate. Significant fragmentation was observed when He was used as the ionizing gas, increasing only slightly with increasing temperature. The N -induced (5 C, 7. L min -1 ) mass spectrum (c) resulted in an abundant [M+NH 4 ] + ion but also considerable fragmentation compared to that of deltamethrin (see Fig. ). Insets in panel (c) show the chemical and isotopic (experi-mental and theoretical) structures of the permethrin pesticide. The inset showing the isotopic distribution corresponds to the [M+NH 4 ] + ion of the nitrogen-induced spectra. Spectral peak assignments and mass accuracies are listed in Table S-1.
This journal is (C) The Royal Society of Chemistry 1 % 1 * (a) 5 1 * (b) 5 15 5 3 35 4 45 5 55 m/z Fig. S He- and N -induced TM-DART spectra of a 55 mg m - deltamethrin-impregnated PermaNet. net. (a) Helium spectrum obtained at 15 C and L min -1 ; (b) N spectrum obtained at 15 C and 7 L min -1. Asterisks indicate the [M+H] + and [M+NH 4 ] + for the He and N spectra, respectively.
This journal is (C) The Royal Society of Chemistry 1 % (a) 1 4 5 6,7 1 3 5 (b) 1 5 3 4 6,7 15 5 3 35 4 m/z Fig. S3 He- and N -induced TM-DART spectra of a 1 mg m - permethrin-impregnated Olyset net. (a) He spectrum obtained at 15 C and L min -1 ; (b) N spectrum obtained at 15 C and 7 L min -1. Spectral peak assignments are consistent with those identified in Figure S-1 and listed in Table S-1.
This journal is (C) The Royal Society of Chemistry 1 a).6 DART Orifice Sample Holder.5.4.3 Orifice Sample Holder DART..1 b) 1...6.4. c) 1. 1.5.9.6.3 d).4. 1.6..4 Fig. S4 CFD simulations at a).5, b) 1., c) 1.5 and d). L min -1 He at 15 ºC when the DART gas nozzle is positioned 4 mm away from the sample holder. The images on the left show a 3D perspective of the system, the middle images show the gas flow from above, and the heat map scales on the right are the gas velocities in m s -1.
This journal is (C) The Royal Society of Chemistry 1 a) Orifice b) DART Sample Holder Orifice Sample Holder DART.7.6.5.4.3..1 1...6.4 c). 1. 1.5.9.6 d).3.4. 1.6..3 Fig. S5 CFD simulations at a).5, b) 1., c) 1.5 and d). L min -1 He at 15 ºC when the DART gas nozzle is positioned in contact with sample holder. The images on the left show a 3D perspective of the system, the middle images show the gas flow from above, and the heat map scales on the right are the gas velocities in m s -1.
This journal is (C) The Royal Society of Chemistry 1 1 6 4.5 1. 1.5..5 Time (min) Fig. S-6 TM-DESI MS analysis of a sample composed of three offset layers of a conventionally-treated bednet coated with 16 mg m - of deltamethrin. Responses for individual strands that were observed in the single-layer sample are no longer observed; however, the greater sample density results in increased response relative to a single-layer sample.
This journal is (C) The Royal Society of Chemistry 1 Table S1 Identified peaks in the DART-TOF MS spectra of the permethrin standard Peak Formula Theoretical Experimental Δm Mass Mass (mmu) 163.76 163.131 5.5 1 [C 7 H 9 Cl ] + 165.46 165.17 6.1 167.17 167..3 [C 13 H 11 O] + 13.4 13.9.4 3 [C 13 H 11 O ] + 199.754 199.761. 355.195 355.197. 4 [M+H-HCl] + 357.166 357.1 1.4 373.757 373.79 4.1 5 [M+H-H O] + 375.77 375.45 11. 377.69 377. 13. 391.6 391.65.3 6 [M+H] + 393.33 393.55.3 395.3 395.911 1. 7 [M] + 39.74 39.4 5. 39.755 39.66 11.1 394.75 394.7 14.7 4.11 4.116.1 [M+NH 4 ] + 41.19 41.117.9 41.169 41.1149.1