VLADIMIR A. NIKIFOROV AND VLADIMIR A. NIKIFOROV. NILU - Norwegian Institute for Air Research, Framsenteret, Tromsø, Norway,

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Molecular design of new derivatizing agents for ultra-sensitive ESI(-) LC-MS-MS determination of non-ionic environmental pollutants of emerging

1 Molecular design of new derivatizing agents for ultra-sensitive ESI(-) LC-MS-MS determination of non-ionic environmental pollutants of emerging concern VLADIMIR A. NIKIFOROV AND VLADIMIR A. NIKIFOROV 3 NILU - Norwegian Institute for Air Research, Framsenteret, Tromsø, Norway, van@nilu.no 1

Starting point: PFOA and other PFCAs bad or

surfactants Acids are strong acids PFOA by

2 Starting point: PFOA and other PFCAs bad or good? Structure optimized Gaussian-9 RB3LYP/6-31+G(d,p) Useful chemicals, stable! Environmental contaminants Anions are good surfactants Acids are strong acids PFOA by LC-MS-MS : Good ionization in ESI Good fragmentation in MS < 1pg/injection 2

3 From Barentsburg, with love: Northernmost LC-MS-MS (courtesy of Mr. Valery Smutin) 3

4 Fluorotelomer alcohols (FTOH) bad or good? FTOHs are not as hazardous as PFCAs (?) FTOHs may yield PFCAs in the environment FTOHs are weak acids, not ionized well in ESI Good for the purpose, bad for the environment, bad in the lab How to make them good again? 4

5 How can we make FTOHs and all other contaminants as good as PFOA for us? Derivatization = conversion to substituted PFOA Test 1: GluF Perfluoroglutaric anhydride 5

6 Testing the idea: GluF = PerfluoroGlutaric Anhydride 3,7-DiMePFOA C 3 F 5 m/z = 131 HC 3 F 6 COO m/z = 195 6:2FTOH-GluF 6:2FTOH-GluF The idea was great indeed But: Reagent volatile, Aggressive (hazard), Moisture-sensitive Derivative not very stable (several hours) 6

7 Optimization of GluF 7

8 Relative Abundance Relative Abundance Relative Abundance Wednesday, 17.: Linda Hanssen et al, Sulfobenzoic anhydride new derivatizing reagent for high sensitivity LC-MSMS analysis of Fluorotelomer alcohols C:\Xcalibur\...\VAN_FTOH_21651_81 5/19/216 11:29:38 AM FTOH-SB, Cal, SB15 lm RT: RT: 5.96 AA: SN: 17 5 NL: 4.83E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 RT: RT: 7.61 AA: 4724 SN: NL: 2.25E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 RT: RT: 7.73 AA: 184 SN: NL: 9.36E2 m/z= F: - c ESI SRM ms2 74. [ , ] M S VAN_FTOH_21651_81 RT: RT: 7.62 AA: 1295 SN: 74 5 RT: 8.23 AA: 32 SN: 18 NL: 6.71E2 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 5.96 AA: SN: 171 NL: 3.77E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.61 AA: 457 SN: 2944 NL: 2.17E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.74 AA: 2112 SN: 492 NL: 1.3E3 m/z= F: - c ESI SRM ms2 74. [ , ] M S VAN_FTOH_21651_81 5 RT: 7.62 AA: 2875 SN: 931 NL: 1.42E3 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 5.95 AA: 797 SN: 187 NL: 1.64E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.62 AA: 4423 SN: 631 NL: 2.8E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.73 AA: 388 SN: 553 NL: 1.52E3 m/z= F: - c ESI SRM ms [ , , , ] M S VAN_FTOH_21651_81 5 RT: 7.62 AA: 1428 SN: 144 RT: 8.23 AA: 272 SN: 3 NL: 7.1E2 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 5.95 AA: 5927 SN: 183 NL: 1.17E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.62 AA: 43 SN: 686 NL: 1.84E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.72 AA: 2977 SN: 74 NL: 1.43E3 m/z= F: - c ESI SRM ms [ , , , ] M S VAN_FTOH_21651_81 5 RT: 7.62 AA: 2994 SN: 248 RT: 7.79 AA: 284 SN: 191 NL: 1.37E3 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 6.99 AA: 7974 SN: 171 NL: 2.54E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 8.3 AA: 3342 SN: 558 RT: 8.14 AA: 6 SN: 99 NL: 1.7E3 m/z= F: - c ESI SRM ms [ , , , ] M S VAN_FTOH_21651_81 5 RT: 7.86 AA: 2336 SN: 531 NL: 1.17E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.76 AA: 1896 SN: 94 RT: 8.38 AA: 298 SN: 18 NL: 9.32E2 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 6.99 AA: 667 SN: 168 NL: 1.93E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 8.3 AA: 3528 SN: 516 RT: 8.14 AA: 936 SN: 124 NL: 1.82E3 m/z= F: - c ESI SRM ms [ , , , ] M S VAN_FTOH_21651_81 5 RT: 7.86 AA: 2965 SN: 788 NL: 1.47E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.76 AA: 353 SN: 611 NL: 1.5E3 m/z= F: - c ESI SRM ms2 71. [ ] M S VAN_FTOH_21651_ 81 5 RT: 6.99 AA: 7675 SN: 166 NL: 2.54E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 8.3 AA: 3375 SN: 7 NL: 1.65E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.85 AA: 2693 SN: 462 NL: 1.37E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.76 AA: 1551 SN: 165 RT: 7.59 AA: 245 SN: 23 RT: 8.38 AA: 23 SN: 23 NL: 7.49E2 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ 81 5 RT: 6.99 AA: 5781 SN: 172 NL: 1.88E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 8.3 AA: 3551 SN: 696 NL: 1.8E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.85 AA: 2876 SN: 125 NL: 1.41E3 m/z= F: - c ESI SRM ms [ , ] M S VAN_FTOH_21651_81 5 RT: 7.75 AA: 3238 SN: 869 NL: 1.56E3 m/z= F: - c ESI SRM ms [ ] M S VAN_FTOH_21651_ Time (min) Time (min) Time (min) :2 FTOH 8:2 FTOH N-MeFOSE N-MeFOSE 6:2 FTOH 1:2 FTOH N-MeFOSA N-MeFOSA Time (min) 8

Dansyl Chloride for derivatization of steroid estrogens: LOQ for EE2 <.35ng/L surface water Thomas, K.V., Langford, K., Reid, M., Vogelsang, C., Øxnevad, S., Bæk, K., Fjeld, E., Brooks, S.

SB vs Dansyl Chloride, FTOH vs Phenolic analytes - SB more reactive in general (DsCl no reaction with FTOH) - SB derivatives are less stable in general (not good for phenolics) - SB reactive centre

9 Dansyl Chloride for derivatization of steroid estrogens: LOQ for EE2 <.35ng/L surface water Thomas, K.V., Langford, K., Reid, M., Vogelsang, C., Øxnevad, S., Bæk, K., Fjeld, E., Brooks, S., Pampanin, D.M., Nikiforov, V., Schlabach, M. (216). Screening programme 215. Pharmaceuticals and hormones (Miljødirektoratet rapport, M-597/216) (NIVA report, ). Oslo: NIVA. SB vs Dansyl Chloride, FTOH vs Phenolic analytes - SB more reactive in general (DsCl no reaction with FTOH) - SB derivatives are less stable in general (not good for phenolics) - SB reactive centre is Carbon (S N 1 type), in DsCl Sulfur (S N 2 type) - Increase of reactivity of DsCl would allow derivatization of tough phenols, while derivatives could still be stable - DFT computations suggest increase of electrophilicity of SO 2 Cl would help 9

10 1,5-Naphthalene Disulfonyl Chloride (15-NDS) up side down Dansyl Chloride - Electron-withdrawing substituent instead of e-donating - Anionic derivative instead of cationic one - Stronger acid instead of weaker base - 2 steps instead of 1 Stable and very well-ionizing derivative 1

11 1,5-NDS derivatives of PBP (Pentabromophenol) and PCP (Pentachlorophenol) Stable and very well-ionizing derivative 15NDS-PCP, 5 pg derivatized 11

12 Highlights A series of derivatization reagents/reactions developed for emerging pollutants Dansylation allowed Ethynylestradiol (EE2) in water below.35ng/l (< EQS) Sulfobenzoic anhydride (SB) allowed sensitive LC analysis of FTOH (tomorrow, Linda Hansen, 17.) Naphthalenedisulfonylchloride (15-NDS) is superior to Dansylchloride and is promising for tougher phenols Perfluoroglutaric anhydride (Glu-F) was not only a model compound: can be used for derivatization of amines, for example All mentioned anionic derivatives are formed merely upon mixing 12

13 To be continued Thank you for your attention! 13

Chapter 07 Haloalkanes

Chapter 07 Haloalkanes 2016 Gregory ook 2016 Gregory ook 2016 Gregory ook 2016 Gregory ook 2016 Gregory ook 2016 Gregory ook hapter 07 aloalkanes Alkyl alides rganic halogen compounds are found in many places from common solvents