Solid Sampling with a Diode Laser for Portable Ambient Mass Spectrometry. Igor V. Veryovkin, 1 and Luke Hanley 1,* Finland

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1 Supporting Information for Solid Sampling with a Diode Laser for Portable Ambient Mass Spectrometry Yeni P. Yung, 1 Raveendra Wickramasinghe, 1 Anu Vaikkinen, 2 Tiina J. Kauppila, 2 Igor V. Veryovkin, 1 and Luke Hanley 1,* 1 Department of Chemistry, University of Illinois at Chicago, Chicago, IL, 60607, USA 2 Division of Pharmaceutical Chemistry and Technology, University of Helsinki, Helsinki, Finland Contents & Preliminary Comments This document contains tentative peak assignments for the spectra of sage leaves (Salvia officinalis) and membrane-grown biofilms of Pseudomonas aeruginosa that are presented in Figures 3 and 4 of the primary manuscript. Tables SI and SII are identical to Tables I and II of the primary manuscript except for the addition of columns for tentative peak assignments. It is important to note that all the peak assignments reported here are only tentative and are based solely on published MS studies (see below). The ±0.5 Da mass error of the field-deployable ion trap used here limits the accuracy of peak assignments. Furthermore, attempts to collect tandem MS data directly from the sage leaves and biofilms have so far proved unsuccessful. Finally, the reference numbers are the same as those cited in the manuscript. S-1

2 Tentative Peak Assignments of Sage Leaf Mass Spectra The tentative peak assignments for LDTD-APPI and LAAPPI mass spectra of sage leaves are given in Table SI and are based on prior GC-MS, LC-MS, and LAAPPI studies Differences in the peaks observed here and previously by LAAPPI 28 might be attributed to the use of different mass analyzers, MS source conditions, and/or sage leaf growth and storage conditions, and/or genetics. The tentative peak assignments are in line with the terpenoid contents of sage leaves The peak at m/z is tentatively attributed to MH + of C 10 H 14, p-cymene; [M-H] + of C 10 H 16, monoterpenes; and/or [MH-H 2 O] + of C 10 H 16 O, a monoterpenoid (see Table SI). The peak at m/z is attributed to M +. of C 10 H 18 O, another monoterpenoid. The peak at m/z is attributed to [M-H] + of C 15 H 24, a sesquiterpene and/or [MH-H 2 O] + of caryophyllene oxide. The peak at m/z is attributed to either M +. of C 15 H 24, a sesquiterpene or [M-H 2 O] + of viridiflorol. The m/z peak is attributed to monoterpene dimers and/or [M-H 2 O] + of manool. For example, previous work 29 found α-pinene (C 10 H 16 ), 1,8-cineole (C 10 H 18 O), α-thujone (C 10 H 16 O), camphor (C 10 H 16 O), β-caryophyllene (C 15 H 24 ), α-humulene (C 15 H 24 ), viridiflorol (C 15 H 26 O) and manool (C 20 H 34 O) to be the most abundant compounds of sage leaf oil extract (referred to as essential oil ). The m/z peak (M +. of C 10 H 16, a monoterpene and/or monoterpenoid) was only observed in LAAPPI while the m/z peak (caryophyllene oxide) was only observed in LDTD-APPI. S-2

3 Table SI. Peaks observed in LAAPPI- and LDTD-APPI-MS spectra of sage leaves with anisole as the dopant. * The letters (a) to (e) annotate peaks observed by both LAAPPI and LDTD- APPI, with tentative assignments based on previous reported phytochemicals. Italicized peaks in LDTD-APPI also appeared with toluene dopant. LAAPPI LDTD- APPI LAAPPI (m/z) from Ref. 28 Tentative Peak Assignments, Refs. 28 and 29 p-cymene MH + (a) (a) *** monoterpenes (e.g., α-pinene/β-pinene/ limonene/camphene) [M-H] + monoterpenoids (e.g., camphor/α-thujone/ β-thujone) [MH-H 2 O] monoterpenes (e.g., α-pinene/β-pinene/ limonene/camphene) M +. monoterpenoids (e.g., borneol/1,8-cineole/terpinen-4-ol) [M-H 2 O] +. (b) (b) monoterpenoids (e.g., borneol/1,8-cineole/terpinen-4-ol) M +. (c) (c) (d) (d) sesquiterpenes (e.g., α-humulene/ β-caryophyllene) [M-H] + caryophyllene oxide [MH-H 2 O] + sesquiterpenes (e.g., α-humulene/ β-caryophyllene) M +. viridiflorol [M-H 2 O] caryophyllene oxide [M-H] + (e) ** (e) monoterpenes (e.g., α-pinene/β-pinene/ limonene/camphene) [2M] +. manool [M-H 2 O] *Peaks were included in Table SI only if they were observed in 50% of the samples with >5 signal to noise (S/N) when compared against the anisole background. **Denotes low S/N peak. ***LDTD-APPI peaks that appear with both anisole and toluene dopant are italicized in Table SI. S-3

4 Tentative Peak Assignments of P. aeruginosa Biofilm Mass Spectra Table SII shows the tentative peak assignments for LDTD-APPI and LAAPPI mass spectra 4, 30- of P. aeruginosa biofilms, based on published results by various mass spectrometric methods. 33 Ion peaks previously attributed to quinolone fragments 30 were observed by both methods, of which ions at m/z were attributed to a fragment ion of 4-hydroxy-2-heptylquinoline (HHQ, C 10 H 9 NO) and m/z to a fragment of 2-heptyl-3-hydoxyquinolone (PQS, C 10 H 9 NO 2 ). Both were observed in secondary ion mass spectra of P. aeruginosa biofilms. 31 The peak observed here at m/z was attributed to a fragment of 4-hydroxy-2-heptylquinoline-N-oxide (HQNO, C 12 H 12 NO) which was previously reported in the tandem MS of quinolones. 24 Peaks were attributed to HAQs at m/z (MH + of C 14 H 15 NO, 4-hydroxy-2-pentenylquinoline) and (MH + of C 18 H 25 NO 2, 2-nonyl-3-hydroxyquinolone, C9-PQS and/or 4-hydroxy-2- nonylquinolone-n-oxide, C9-NQNO) were additionally observed in both LAAPPI and LDTD- APPI mass spectra. Furthermore, the peak at m/z was attributed to 1-hydroxyphenazine (MH + of C 12 H 8 N 2 O, 1-HP) while m/z was attributed to 1-methoxyphenazine and/or pyocyanin (M +. of C 13 H 10 N 2 O, 1-MP and/or PYO). 4, 31 A peak attributed to HSL at m/z was thought to be an oxidative product of C6-HSL (MH + of C 10 H 18 N 2 O 7 ). 33 S-4

5 Table SII. Peaks observed from P. aeruginosa biofilms by LAAPPI and LDTD-APPI. * Peaks 4, marked (a) to (g) were tentatively assigned to previously reported metabolites. LAAPPI LDTD-APPI Tentative Peak Assignments Monoisotopic Mass (Da) of Assignment Refs. (a) (a) (b) (b) (c) (c) ** HAQ (hydroxy-alkyl-quinolones) fragment ion of HHQ (4-hydroxy-2-heptylquinoline) HAQs fragment ion of PQS (Pseudomonas quinolone signal; 2-heptyl-3-hydroxyquinolone) HAQs fragment ion of HQNO (4-hydroxy-2- heptylquinoline-n-oxide) , , (d) (d) HP (1-hydroxyphenazine) MH ** (e) (e) MP (1-methoxyphenazine) M +. PYO (pyocyanin) M (f) (f) hydroxy-2-pentenylquinoline MH (g) (g) ** C6-HSL (N-hexanoyl-homoserine lactone) oxidative product MH nonyl-3-hydroxyquinolone (C9-PQS) MH + 4-hydroxy-2-nonylquinolone-N-oxide (C9-NQNO) MH , *Peaks were included in Table SII only if they were observed in 50% of the samples with >5 signal to noise (S/N) when compared against the toluene background. **denotes low S/N peak. S-5

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