Molecular Characterization of Ongoing Enzymatic Reactions in Raw Garlic Cloves Using Extractive

Supporting Information

Preconcentration of organic solutes in urine by bubble bursting

S-1 Supplementary Tables

Table S-1. Signal enrichment factor (R = Ibubble/Ibulk) of phenylalanine (Phe, 100 µM) and arginine (Arg, 20 µM) in aqueous solutions by bursting bubbles produced using diffusers with different porosity. Bubble path length was 100 cm.

Table S-2. Signal enrichment factor (R = Ibubble/Ibulk) of Arg in aqueous solution (20 µM) by bursting bubbles produced using diffusers with different porosity depending on the path length of rising bubbles. Mode 1 = porosity 100 µm; mode 2 = porosity 1-10 µm; mode 3 = porosity 0.2-5 µm.

S-2 Table S-3. Urine metabolites detected by the high-resolution mass spectrometry of aerosols produced by bubble bursting. *Identification additionally verified by tandem mass spectrometry of authentic compound. **HMDB chemical classification was used. See Table S-4. No HMDB ID Formula R[M+H]+ R[M+Na]+ MS/MS* Chemical category** 1 15334 C17H27NO4 10.1±1.1 + 1-1-0 2 14592 C19H29NO5 9.1±1.3 1-2-1 3 15639 C17H23N3O 7.4±1.2 1-2-2 4 14531 C19H29NO 1-2-2 5 15374 C24H34N2O 1-2-2 6 13835 C16H22O4 6.8±1.2 0.9±0.3 1-2-3 7 02107 C8H6O4 6.0±0.9 1-2-3 8 14018 C12H18O2 6.7±1.2 1-2-4 9 14956 C12H18O 1-2-4 10 29226 C12H14O4 4.4±0.8 1-2-5 11 00118 C9H10O4 1-2-5 12 15145 C10H16NO 1-2-5 13 14538 C14H18N4O3 1-2-6 14 15114 C17H25NO3 1-2-7 15 15039 C13H12Cl2O4 1-2-8 16 14909 C22H26NO3 1-2-9 17 13973 C22H31NO2 1-2-9 18 14708 C26H28N2 1-2-9

S-3 19 15589 C26H26F2N2 1-2-9 20 15120 C24H28ClN5O3 1-2-9 21 14486 C32H41NO2 1-2-9 22 15590 C29H31F2N3O 1-2-9 23 60905 C21H21ClFNO 1-2-10 24 13961 C26H36N2O4 1-2-10 25 01850 C27H38N2O4 1-2-10 26 15406 C20H27N5O5S 1-2-11 27 13862 C28H29N7O 1-2-12 28 15631 C25H32N2O4 0.7±0.1 2-1-1 29 15543 C21H33N3O5S 9.5±1.3 2-1-1 30 00001 C7H11N3O2 8.4±1.3 + 2-1-1 31 00194 C10H16N4O3 8.0±1.3 1.5±0.3 + 2-1-1 32 00177 C6H9N3O2 5.4±0.5 + 2-1-1 33 00182 C6H14N2O2 5.3±0.5 + 2-1-1 34 04827 C7H13NO2 2-1-1 35 14388 C24H33N3O4 2-1-1 36 00791 C15H29NO4 15±0.9 3-1-1 37 13205 C17H31NO4 12.3±1.1 3-1-1 38 02013 C11H21NO4 11.3±1.1 0.7±0.2 3-1-1 39 00378 C12H23NO4 7.8±1.3 3-1-1 40 34708 C11H18O2 7.2±1.1 3-1-1 41 00756 C13H25NO4 3-1-1 42 00651 C17H33NO4 3-1-1 43 13330 C21H39NO5 13.5±1.3 3-1-2 44 60682 C8H12O2 10.9±1.2 3-1-2 45 00784 C9H16O4 9.8±1.3 3-1-2 46 00482 C8H16O2 8.0±1.3 3-1-2 47 59731 C7H8O4 3-1-2 48 00341 C8H12O4 3-1-2 49 00933 C12H20O4 3-1-2 50 00394 C14H26O5 3-1-2 51 02183 C22H32O2 3-1-2 52 01220 C20H32O5 11.7±1.1 + 3-1-3 53 05079 C20H28O3 3-1-3 54 03876 C20H32O3 3-1-3 55 01085 C20H32O4 3-1-3 56 01139 C20H34O5 3-1-3 57 04238 C20H30O4 3-1-3 58 02277 C18H30O6 3-1-3 59 02904 C18H30O6 1.7±0.3 3-1-3 60 00526 C21H34O5 14.1±0.4 3-2-1 61 00903 C21H32O5 13.2±1.2 3-2-1 62 00037 C21H28O5 12.7±1.1 + 3-2-1

S-4 63 61016 C21H28O6 3-2-1 64 61106 C25H34O7 3-2-1 65 02472 C32H51NO12 12±1.0 3-2-2 66 10320 C27H42O11 11.5±1.0 3-2-2 67 02829 C25H38O8 3-2-2 68 02596 C30H48O10 3-2-2 69 00374 C21H30O3 3-2-3 70 00315 C21H32O3 3-2-3 71 60708 C24H29ClO5 3-2-3 72 15181 C26H32F2O7 3-2-3 73 15676 C27H34F2O7 3-2-3 74 00053 C19H26O2 3-2-4 75 00077 C19H28O2 3-2-4 76 15446 C21H26O2 3-2-5 77 14511 C21H28O2 3-2-5 78 01926 C20H24O2 3-2-5 79 14855 C20H26O2 3-2-5 80 00380 C19H26O3 3-2-5 81 15327 C23H31Cl2NO3 3-2-5 82 14972 C29H35NO2 3-2-6 83 14652 C43H66O14 3-2-7 84 13817 C14H20O2 6.5±1.1 3-3-1 85 04586 C10H14O2 5.7±0.6 3-3-1 86 01878 C10H14O 5.5±0.5 3-3-1 87 32913 C13H22O 3-3-2 88 15643 C16H26O5 3-3-2 89 04808 C18H18O4 3-3-3 90 04602 C21H26O3 3-3-4 91 03141 C26H36O8 3-3-5 92 10344 C34H52O7 3-3-6 93 15293 C19H25N5O4 10.5±1.1 1.4±0.3 4-1-1 94 61107 C21H31N5O3 4-1-1 95 15488 C30H26F6N4O2 4-1-1 96 15194 C20H23N5O6S 9.4±1.4 4-2-1 97 14723 C12H21N5O2S2 9.0±1.3 0.7±0.1 4-3-1 98 14934 C24H20N6O3 4-3-2 99 13845 C25H30N6O2 4-3-2 100 00562 C4H7N3O 8.7±1.3 + 4-4-1 101 14862 C14H16N4 8.6±1.3 4-5-1 102 14746 C18H26ClN3 4-5-1 103 14668 C20H29N3O2 4-5-2 104 04158 C33H42N4O6 8.5±1.3 1.3±0.1 + 4-6-1 105 13824 C9H14O 7.9±1.3 4-7-0 106 35907 C10H18O2 7.6±1.2 4-8-0

S-5 107 14868 C10H7N3S 7.5±1.1 + 4-9-0 108 04193 C7H8N2O2 6.3±1.1 1.4±0.2 + 4-10-1 109 14597 C15H21NO2 6.3±1.0 + 4-11-1 110 15238 C26H29FN2O2 4-11-1 111 15400 C8H8N4 4-12-1 112 15104 C17H18N4O 4-13-1 113 14671 C22H23N3O4 4-13-2 114 15267 C24H26N2O4 4-13-2 115 14864 C20H26N2 4-14-1 116 60717 C25H32N2O7 4-14-1 117 14629 C24H36O3 4-15-1 118 15172 C23H29N3O2S 4-16-1 119 61012 C20H18F7NO2 4-17-1 120 00451 C8H14O3 9.7±1.3 5-1-1 121 29165 C7H12O2 9.2±1.4 5-2-1 122 13821 C9H18O 5-2-1 123 60705 C21H22N4O8 7.9±1.4 5-3-1 124 60498 C16H24N3O8 5-3-1 125 00122 C6H12O6 6.7±1.2 + 5-3-2 126 15090 C21H41N5O7 5-3-3 127 14936 C21H43N5O7 5-3-3 128 00158 C9H11NO3 5.0±0.4 1.2±0.1 + 6-1-0 129 14913 C22H36N2O5S 6-1-0 130 29865 C9H6O3 4.2±1.0 6-2-1 131 15487 C19H15NO6 6-2-1 132 02899 C14H6O8 6-3-1 133 15593 C27H42N2O5S 6-4-1

Table S-4. Chemical categories of urine metabolites in Table S-3 according to HMDB classification. superclass class subclass 1 Benzenoids 1-1 Tetralins 1-2 Benzene and 1-2-1 Phenol esters

S-6 substituted derivatives 1-2-2 Phenylmethylamines 1-2-3 Benzoic acids and derivatives 1-2-4 Cumenes 1-2-5 Phenols and derivatives 1-2-6 Phenol ethers 1-2-7 Phenylacetic acid derivatives 1-2-8 Phenoxyacetic acid derivatives 1-2-9 Diphenylmethanes 1-2-10 Phenylbutylamines 1-2-11 Benzenesulfonamides 1-2-12 Benzamides 2 Organic acids 2-1 Carboxylic acids 2-1-1 Amino acids, and derivatives and derivatives peptides, and analogues 3 Lipids and 3-1 fatty acyls 3-1-1 fatty acid esters lipid-like molecules 3-1-2 Fatty acids and conjugates 3-1-3 Eicosanoids 3-2 Steroids and 3-2-1 Hydroxysteroids steroid derivatives 3-2-2 Steroidal glycosides 3-2-3 Pregnane steroids 3-2-4 Androstane steroids 3-2-5 Estrane steroids 3-2-6 Oxosteroids 3-2-7 Steroid lactones 3-3 Prenol lipids 3-3-1 Monoterpenoids 3-3-2 Sesquiterpenoids 3-3-3 Quinone and hydroquinone lipids 3-3-4 Retinoids 3-3-5 Terpene glycosides 3-3-6 Triterpenoids 4 4-1 Diazinanes 4-1-1 Piperazines

S-7 Organoheterocycli c compounds 4-2 Lactams 4-2-1 Beta lactams 4-3 Azoles 4-3-1 Thiazoles 4-3-2 Tetrazoles 4-4 Azolines 4-4-1 Imidazolines 4-5 Quinolines and 4-5-1 Aminoquinolines derivatives and derivatives 4-5-2 Quinoline carboxamides 4-6 Tetrapyrroles and 4-6-1 Bilirubins derivatives 4-7 Heteroaromatic compounds 4-8 Oxolanes 4-9 Benzimidazoles 4-10 Pyridines and 4-10-1 derivatives Pyridinecarboxylic acids and derivatives 4-11 Piperidines 4-11-1 Phenylpiperidines 4-12 Naphthyridines 4-12-1 Phthalazines 4-12-2 Quinazolines 4-13 Indoles and 4-13-1 Indoles derivatives 4-13-2 Carbazoles 4-14 Benzazepines 4-14-1 Dibenzazepines 4-15 Naphthopyrans 4-15-1 Naphthopyranones 4-16 Benzothiazines 4-16-1 Phenothiazines 4-17 Oxazinanes 4-17-1 Morpholines 5 Organooxygen 5-1 Alcohols and 5-1-1 Secondary alcohols compounds polyols 5-2 Carbonyl compounds 5-2-1 Ketones 5-3 Carbohydrates and 5-3-1 Sugar acids and carbohydrate conjugates derivatives 5-3-2 Monosaccharides 5-3-3 Aminosaccharides 6 6-1 Phenylpropanoic Phenylpropanoids acids and polyketides 6-2 Coumarins and 6-2-1 Hydroxycoumarins derivatives 6-3 Tannins 6-3-1 Hydrolyzable tannins

S-8 6-4 Macrolides and 6-4-1 Epothilones and analogues analogues

Table S-5. The enrichment of signal intensity (R) and signal-to-noise ratio (S/N) for clenbuterol (Cle) and salbutamol (Sal) in urine by bubble bursting with different gases. Detection was done on LTQ-MS.

Supplementary Figure

S-9 Fig. S-1 Signal enrichment (R = Ibubble/Ibulk) for the protonated species of urine metabolites across m/z domain.