Supplementary information

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1 Supplementary information An Optoelectronic Nose for Detection of Toxic Gases Sung H. Lim, Liang Feng, Jonathan W. Kemling, Christopher J. Musto, Kenneth S. Suslick * Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois USA and isense LLC, 470 Ramona St., Palo Alto, CA USA (ksuslick@illinois.edu). Contributed equally to this work. *Corresponding author. locking snaps dual elastomer gaskets mm 9 mm 25 puncturable elastomer seals inlet outlet Fig. S1 Photographs of cartridged colorimetric sensor arrays, all on the same scale. Left: standard disposable cartridge used in these studies; the inside dimensions are 22x22x4 mm with a total dead volume ~2 ml. Middle: disposable low dead-volume selfsealing cartridge with the colorimetric sensor array printed directly on a PET (polyethylene terephthalate) flat. Right: close-up of the low dead-volume printed colorimetric sensor array and sealing system. The total head-space volume of the low dead-volume cartridge is ~150 L (i.e., >10-fold smaller volume). The cartridges are produced by standard injection molding. nature chemistry 1

2 exhaust inlet disposable sensor array PC on a chip: Toradex Colibri PXA320; 0.8 GHz, 1GB, USB, WiFi, GPS. Touchscreen: Sharp WQVGA TFT Needle Injector Board Micron CMOS camera (white LED below) Parker micropump 4 4 AA or Rechargeable Li batteries hidden behind injector board Fig. S2 Labeled photographs of a functional handheld prototype of the optoelectronic nose. Left: the fully assembled unit; center: with top cover removed; right: top electronics board and touchscreen display lifted vertically to the right. The disposable sensor array used with this prototype is shown in Figure S1. The image quality of this prototype is considerably improved compared to the flat bed scanners used in this study (Epson Perfection V200); an improvement in S/N of a factor of 3 has been achieved even at this early stage of development. TICS Pre- mixed Certified MFC 1 MKS digital mass flow controllers MFC 2 Diluted TICs vent MKS Multi-Gas Analyzer (in-line FTIR analysis) Dry N 2 Gas MFC 3 Switch N 2 Gas MFC 4 Wet N 2 Gas 100 % RH MFC 5 Control flatbed scanner with flow cell sensor array cartridge N 2 Gas H 2 O Fig. S3 Gas mixing rig used for exposure of colorimetric sensor arrays. The box labeled switch is actually a series of three three-way valves, which allows for venting and also diversion of analyte stream to the MKS multi-gas analyzer. nature chemistry 2

3 10% RH ~2,000 ppm 30% RH 50% RH 70% RH 90% RH ~18,000 ppm Fig. S4 The colorimetric sensor array is unaffected by humidity over a wide range. There is essentially no response to variations in humidity from 10% to 90% RH; average of three trials is shown. For display purposes, the color range of these difference maps is expanded from 4 to 8 bits per color (RGB range of 4-19 expanded to 0-255) Cumulative Variance (%) PCA Eigenvector Number Fig. S5 Scree plot of the principal components from PCA of 140 trials using 19 TICs and a control. The colorimetric sensor array has an extraordinarily high level of dispersion: 9 dimensions are required to define 90% of the total variance, 13 dimensions for 95% of the total variance, and 23 dimensions for 99%. nature chemistry 3

4 Table S1. List of chemically responsive colorants. Spot # Name 1 5,10,15,20-tetraphenylporphyrinatozinc(II) 2 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphyrinatozinc(II) 3 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatozinc(II) 4 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphyrinatocobalt(II) 5 5,10,15,20-tetraphenylporphyrinatocadmium(II) 6 5,10,15,20-tetraphenylporphyrinatochromium(III) chloride 7 Bromophenol Blue + TBAH 8 Methyl Red + TBAH 9 Chlorophenol Red + TBAH 10 Nitrazine Yellow + TBAH 11 Bromothymol Blue + TBAH 12 Thymol Blue + TBAH 13 m-cresol Purple + TBAH 14 Zn(OAc) 2 + m-cresol Purple + TBAH 15 HgCl 2 + Bromophenol Blue + TBAH 16 HgCl 2 + Bromocresol Green + TBAH 17 Pb(OAc) [4-[[4-(dimethylamino)phenyl]azo]phenyl]-2,2,2-trifluoroethanone + TsOH 19 -Naphthol Red + TsOH 20 Tetraiodophenolsulfonephthalein 21 Fluorescein 22 Bromocresol Green 23 Methyl Red 24 Bromocresol Purple 25 Bromophenol Red 26 Rosolic Acid 27 Bromopyrogallol Red 28 Pyrocatechol Violet 29 Nile Red 30 Disperse Orange # (4-Nitrobenzyl)pyridine + N-Benzylaniline 32 4-[2-[4-(dimethylamino)phenyl]ethenyl]-2,6-dimethylpyrylium 33 LiNO 3 + Cresol Red 34 Acridine Orange Base 35 AgNO 3 + Bromophenol Blue 36 AgNO 3 + Bromocresol Green Spot numbering from left to right, top to bottom for 6x6 array shown in Figure 1. TBAH: 1.0 M tetrabutylammonium hydroxide in 2-methoxyethanol TsOH: 1.0 M p-toluenesulfonic acid in 2-methoxyethanol nature chemistry 4

5 Table S2. Molecular formula of TICs and their IDLH concentrations Name Molecular Formula IDLH (ppm) Ammonia NH Arsine AsH 3 3 Chlorine Cl 2 10 Diborane B 2 H 6 15 Dimethylamine (CH 3 ) 2 NH 500 Fluorine F 2 25 Hydrogen Chloride HCl 50 Hydrogen Cyanide HCN 50 Hydrogen Fluoride HF 30 Hydrogen Sulfide H 2 S 100 Hydrazine N 2 H 4 50 Methylamine CH 3 NH Methylhydrazine CH 3 NHNH 2 20 Nitric acid HNO 3 25 Nitrogen Dioxide NO 2 20 Phosgene COCl 2 2 Phosphine PH 3 50 Sulfur Dioxide SO Trimethylamine (CH 3 ) 3 N 200 nature chemistry 5

6 Table S3. Color difference database for 19 TICs and a control R1 G1 B1 R2 G2 B2 R3 G3 B3 R4 G4 B4 R5 G5 B5 R6 G6 B6 R7 G7 B7 R8 G8 B8 R9 G9 B9 NH NH NH NH NH NH NH Arsine Arsine Arsine Arsine Arsine Arsine Arsine Cl Cl Cl Cl Cl Cl Cl Control Control Control Control Control Control Control Diborane Diborane Diborane Diborane Diborane Diborane Diborane (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH F F F F F F F HCl HCl HCl HCl HCl HCl HCl nature chemistry 6

7 R1 G1 B1 R2 G2 B2 R3 G3 B3 R4 G4 B4 R5 G5 B5 R6 G6 B6 R7 G7 B7 R8 G8 B8 R9 G9 B9 HCN HCN HCN HCN HCN HCN HCN HF HF HF HF HF HF HF H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH HNO HNO HNO HNO HNO HNO HNO NO NO NO NO NO NO NO nature chemistry 7

8 R1 G1 B1 R2 G2 B2 R3 G3 B3 R4 G4 B4 R5 G5 B5 R6 G6 B6 R7 G7 B7 R8 G8 B8 R9 G9 B9 Phosgene Phosgene Phosgene Phosgene Phosgene Phosgene Phosgene Phosphine Phosphine Phosphine Phosphine Phosphine Phosphine Phosphine SO SO SO SO SO SO SO (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N nature chemistry 8

9 R10 G10 B10 R11 G11 B11 R12 G12 B12 R13 G13 B13 R14 G14 B14 R15 G15 B15 R16 G16 B16 R17 G17 B17 R18 G18 B18 NH NH NH NH NH NH NH Arsine Arsine Arsine Arsine Arsine Arsine Arsine Cl Cl Cl Cl Cl Cl Cl Control Control Control Control Control Control Control Diborane Diborane Diborane Diborane Diborane Diborane Diborane (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH F F F F F F F HCl HCl HCl HCl HCl HCl HCl nature chemistry 9

10 R10 G10 B10 R11 G11 B11 R12 G12 B12 R13 G13 B13 R14 G14 B14 R15 G15 B15 R16 G16 B16 R17 G17 B17 R18 G18 B18 HCN HCN HCN HCN HCN HCN HCN HF HF HF HF HF HF HF H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH HNO HNO HNO HNO HNO HNO HNO NO NO NO NO NO NO NO nature chemistry 10

11 R10 G10 B10 R11 G11 B11 R12 G12 B12 R13 G13 B13 R14 G14 B14 R15 G15 B15 R16 G16 B16 R17 G17 B17 R18 G18 B18 Phosgene Phosgene Phosgene Phosgene Phosgene Phosgene Phosgene Phosphine Phosphine Phosphine Phosphine Phosphine Phosphine Phosphine SO SO SO SO SO SO SO (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N (CH 3 ) 3 N nature chemistry 11

12 R19 G19 B19 R20 G20 B20 R21 G21 B21 R22 G22 B22 R23 G23 B23 R24 G24 B24 R25 G25 B25 R26 G26 B26 R27 G27 B27 NH NH NH NH NH NH NH Arsine Arsine Arsine Arsine Arsine Arsine Arsine Cl Cl Cl Cl Cl Cl Cl Control Control Control Control Control Control Control Diborane Diborane Diborane Diborane Diborane Diborane Diborane (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH (CH 3 ) 2 NH F F F F F F F HCl HCl HCl HCl HCl HCl HCl nature chemistry 12

13 R19 G19 B19 R20 G20 B20 R21 G21 B21 R22 G22 B22 R23 G23 B23 R24 G24 B24 R25 G25 B25 R26 G26 B26 R27 G27 B27 HCN HCN HCN HCN HCN HCN HCN HF HF HF HF HF HF HF H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S H 2 S Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine Hydrazine CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH CH 3 NHNH HNO HNO HNO HNO HNO HNO HNO NO NO NO NO NO NO NO nature chemistry 13