Electronic Supplementary Material (ESI) for Analyst. This journal is © The Royal Society of Chemistry 2015
SUPPLEMENTARY INFORMATION Solvatochromic sensor array for the identification of common organic solvents Jacqueline M. Rankin*, Qifan Zhang*, Maria LaGasse, Yinan Zhang, Jon R. Askim and Kenneth S. Suslick† † Department of Chemistry, University of Illinois at Urbana-Champaign, 600South Mathews Avenue, Urbana, Illinois, 61801, USA. E-mail:
[email protected] *Contributed equally.
Experimental procedure: Eighteen spots were printed on polypropylene membrane (0.2 μm pore size, Sterlitech Corporation). Seven solvatochromic dyes, including 4 positive solvatochromic dyes (Nile Red, Disperse Orange 25, Disperse Orange 3, and Phenol Blue) and 3 negative solvatochromic dyes (Merocyanine 540, Reichardt’s Dye and 1-Ethyl-4-(2-hydroxystyryl)pyridinium iodide), were used. All dyes and solvents were reagent grade, obtained from Sigma-Aldrich, and used without further purification. For colorimetric sensor array printing, the formulations were loaded into an 18–hole Teflon ink well (40 µL). Sensor arrays were printed using an array of 18 floating slotted pins arranged linearly; pins were dipped into the ink well and brought into contact with the polypropylene membrane, transferring to membrane ~400 μm diameter spots of each formulation. The printing protocol for spots used in the collection of diffuse reflectance spectra is the same as above except larger diameter floating slotted pins were used to print ~1 mm diameter spots (equivalent to the approximate read diameter of the reflectance probe). Once printed, all arrays were stored in a glove bag under nitrogen for more than 3 days to ensure evaporation of solvent vapors. Three mass flow controllers were used to control the total flow rate passing over the colorimetric sensor array. The total flow rate was 500 sccm and the analyte concentration was 10% (v/v) its saturated vapor pressure. The analyte concentration was obtained by flowing nitrogen at 50 sccm through a bubbler with 40 ml of pure solvent. This saturated stream was diluted with dry nitrogen for a total flow of 500 sccm using another mass flow controller. Typically, a dry nitrogen control stream (500 sccm) was passed over the array for two minutes, followed by five minutes of analyte flow. Images of the array were collected using a flatbed scanner after 2 min of dry nitrogen and after 5 min of analyte exposure. The RGB values for the pixels corresponding to the center two-thirds of each spot were averaged to avoid spot edge artifacts using a customized software package, SpotFinder (iSense). All experiments were run in quintuplicate. For each trial, a color change profile was obtained by subtracting the RGB values of the “before” image (2 min dry nitrogen) from the “after” image (5 min analyte). This yields a 54-dimensional vector (i.e., 18 changes in red, green, and blue values) that quantitatively describes the color change of the array upon exposure to an analyte; this vector, or color pattern, is unique for each analyte. The color change profiles were compiled into a library database; standard chemometric analyses including principal component analysis (PCA) and hierarchical cluster analysis (HCA) were performed on the database using a multi-variance statistical package (MVSP, Kovach Computing Services). For all HCA, minimum variance (i.e., Ward’s method) was used for classification. Diffuse reflectance spectra were obtained using a B&W tek Prime-X spectrometer with 2.5 nm resolution, a reflectance accessory from StellarNet, Inc. with seven 400 µm illuminating fibers and a 600 µm read fiber in a 7 around 1 configuration and a deuterium/tungsten light source (190-1100 nm). Each spectrum was processed by first removing 4 points (from 485.35487.76 nm) and 8 points (from 654.08-659.42 nm) due to the presence of hydrogen emission lines (characteristic of the deuterium light source), which would distort the signal in those regions. Next, each spectrum was put through a 20-point Savitzky-Golay smoothing filter. Figure 4a was also normalized from 0-1 to more clearly illustrate the observed wavelength shift.
Table S1. A summary of solvatochromic dyes and their categories. Number
Solvatochromic Category
Dye name (abbreviation)
1
positive
Nile Red (NR)
2
positive
Disperse Orange #25 (DO25)
3
positive
Disperse Orange #3 (DO3)
4
positive
N,N-Dimethylindoaniline (Phenol Blue, PB)
5
negative
Merocyanine 540 (M540)
6
negative
Reichardt’s Dye (R)
7
negative
1-Ethyl-4-(2-hydroxystyryl)pyridinium Iodide (EHPI)
Molecular Structure
Table S2. A summary of matrices and their concentrations for printing. Name A B C D a
Class polar hydrogen bonding polar hydrophobic (ionic liquid) relative nonpolar hydrophobic non-polar hydrophobic
ME =2-methoxyethanol
Composition
Concentration (v/v% in MEa)
Glycerol
10
1-Butyl-3-methylimidazolium Hexafluorophosphate
10
Benzyl Butyl Phthalate
30
Dow Diffusion Oil
10
Table S3. A complete list of solvatochromic dye-matrix combination. Spot # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Dye NR NR NR DO25 DO25 DO25 DO3 DO3 DO3 PB PB PB M540 M540 R R EHPI EHPI
Amount (mg) 1 1 1 5 5 5 10 10 8 3 5 3 1.5 1.5 15 15 2 4
Matrix A B C A B C A B C A B C C D C D C D
Table S4. Summary of chosen analytes and their empirical ET(30) values. Analyte Name 1 2 3 4 5 6 7 8 9 10 11
Benzene 1,4-Dioxane 1,1,1-Trichloroethane Tetrahydrofuran 1,2-Dibromoethane Acetone Dimethyl Formamide Dimethyl Sulfoxide 1-Hexanol Ethanol Water
ET(30) (kcal·mol-1) 34.3 36.0 36.2 37.4 38.3 42.2 43.2 45.1 48.8 51.9 63.1
Pyridine ET(30) = 40.5 Cyclohexanone ET(30) = 39.8 2- methylbutane ET(30) = 30.9 Cyclohexane ET(30) = 30.9 Decane ET(30) = 31.0 2,4-dimethyl-3-pentanol ET(30) = 40.1 0
1
2
4
30
Squared Euclidean Distance / 100000
Figure S1. Hierarchical cluster analysis of the colorimetric array response to two groups of three common organic solvents with similar ET(30) values (given in kcal·mol-1) at 10% of their saturation vapor pressure after 5 min of exposure. Each analyte was run in triplicate. The HCA used minimum variance (i.e., Ward’s method) for clustering. Clustering appears independent of ET(30) and even analytes with the same ET(30) value are clearly separable, further demonstrating the colorimetric array probes more than just solvent polarity.
sensor spot # 1
Pyridine
2
3
4
,5
6
7
8
9
10 11
12
13 14
15 16
17
18
ET(30) = 40.5
2,4-dimethyl-3-pentanol
ET(30) = 40.1
Cyclohexanone
ET(30) = 39.8
Decane
ET(30) = 31.0
2- methylbutane
ET(30) = 30.9
Cyclohexane
ET(30) = 30.9
Figure S2. Difference maps showing the colorimetric sensor array response to two groups of three common organic solvents with similar ET(30) values (given in kcal·mol-1) at 10% of their saturation vapor pressure after 5 min of exposure (averages of three trials each are shown). A color range of 1.5 - 8.5 was expanded to 8-bit color range (i.e., 0-255) for visualization. Response patterns show no obvious correlation to the analytes’ ET(30) value.
sensor spot # 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Difference Map Before Exposure Images After Exposure Images mostly chemical mostly physical
mostly physical
mostly physical
mostly physical chemical & physical
mostly chemical chemical chemical & physical & physical
Figure S3. A typical array response for the solvatochromic sensor array. This particular experiment shows the response to 2,4-dimethyl-3-pentanol at 10% of its saturation vapor pressure. Top: difference map of 5 minute exposure time with color range of 1.5 - 8.5 expanded to 8-bit color range (i.e., 0-255) for visualization. Middle: raw images before exposure. Bottom: raw images after 5 minutes of exposure. Given below the images is the assignment of the primary reason for changes in RGB values: color changes are attributable to both chemical (i.e., analyte-dye interactions) and physical (i.e., spot blooming and refractive index alteration) changes.
0% humidity control_1 0% humidity control_2 0% humidity control_3 0% humidity control_4 0% humidity control_5 0% humidity control_6 0% humidity control_7 1,4-dioxane_1 1,4-dioxane_2 1,4-dioxane_3 1,4-dioxane_4 1,4-dioxane_5 1,1,1-trichloroethane_1 1,1,1-trichloroethane_2 1,1,1-trichloroethane_3 1,1,1-trichloroethane_4 1,1,1-trichloroethane_5 acetone_1 acetone_2 acetone_3 acetone_4 acetone_5 1,2-dibromoethane_1 1,2-dibromoethane_2 1,2-dibromoethane_3 1,2-dibromoethane_4 1,2-dibromoethane_5 DMF_1 DMF_2 DMF_3 DMF_4 DMF_5 DMSO_1 DMSO_2 DMSO_3 DMSO_4 DMSO_5 ethanol_1 ethanol_2 ethanol_3 ethanol_4 ethanol_5 THF_1 THF_2 THF_3 THF_4 THF_5 1-hexanol_1 1-hexanol_2 1-hexanol_3 1-hexanol_4 1-hexanol_5 benzene_1 benzene_2 benzene_3 benzene_4 benzene_5 water_1 water_2 water_3 water_4 water_5
4 3 2 1 -1.18 -3.44 -0.85 -13.19 8.40 -4.01 3.00 3.57 -1.20 6.15 5.85 -0.03 -1.30 0.28 -5.83 -5.00 -5.50 4.62 10.97 -7.97 -2.43 1.54 4.13 -11.78 1.81 -5.87 -0.16 -5.69 6.87 10.79 17.28 106.69 -8.64 1.08 2.12 84.18 6.68 6.09 6.24 76.72 1.51 8.92 9.64 90.15 1.13 17.73 12.94 93.00 -1.79 1.03 -17.13 -20.97 -10.64 2.00 -5.84 -24.43 0.75 -4.06 -5.67 -5.46 -7.19 0.11 -10.00 -14.54 -1.40 5.73 -9.03 -12.60 4.04 -6.94 9.23 154.91 7.08 12.91 16.43 154.65 9.11 1.49 2.85 116.50 23.17 25.87 28.49 147.66 28.20 17.86 16.52 171.75 13.99 45.12 56.78 52.27 6.47 5.22 6.75 26.55 -1.70 9.32 14.70 22.02 19.97 23.25 28.13 39.69 0.83 12.30 12.18 27.75 21.99 13.05 -1.32 370.45 17.32 4.34 7.90 343.41 14.46 6.00 1.31 335.81 8.81 4.77 -3.50 374.84 9.72 1.84 2.17 254.54 19.21 7.93 -0.80 187.40 21.83 23.34 28.01 192.62 16.90 24.62 22.60 167.55 19.31 18.63 16.60 182.52 20.52 15.64 13.61 190.01 20.03 19.35 11.85 9.30 16.99 17.63 14.91 -0.73 19.70 16.85 20.41 24.00 21.26 29.52 26.03 13.95 21.84 11.90 18.60 22.43 -10.00 -7.24 -3.03 -66.27 -18.54 -9.84 -6.43 -83.83 -9.51 1.30 -9.40 -58.38 -7.08 -0.75 10.70 -66.22 -9.46 -5.89 0.65 -66.59 -6.54 -23.14 -8.27 -4.43 2.86 -6.22 -13.19 14.81 -9.68 1.62 -1.03 20.70 -10.59 -1.51 -7.62 -1.51 -3.78 -8.49 -1.68 1.35 -1.32 14.70 31.91 29.07 1.18 7.45 6.92 60.58 15.38 25.58 46.09 53.85 5.05 19.76 30.40 52.61 5.07 16.87 28.83 49.03 2.17 0.03 -6.28 10.98 -1.89 -0.45 1.32 -3.30 -5.05 3.21 6.47 -7.65 -0.94 3.26 -2.17 -5.36 -3.33 -9.68 -3.80 -10.69
5 8.38 2.01 22.51 6.42 18.71 12.57 2.57 -74.13 -78.38 -57.89 -62.79 -40.75 30.65 14.81 20.17 -0.86 10.86 -149.02 -124.65 -74.66 -60.16 -125.45 3.40 -42.43 -28.69 4.30 -7.51 -319.03 -294.73 -285.83 -336.42 -193.13 -76.16 -73.35 -62.40 -70.64 -74.75 4.94 3.94 -1.80 20.25 8.38 52.65 56.65 39.95 35.73 43.78 -6.81 -24.00 -22.81 0.00 -8.86 13.73 -52.82 15.79 -31.18 -13.62 -17.84 -8.74 3.37 -2.21 -4.84
6 5.50 2.43 11.61 5.05 10.60 -3.63 -4.29 4.51 -8.17 0.59 3.57 17.34 -11.24 -14.17 -6.27 -16.17 -15.78 -17.35 -12.15 -15.81 16.57 -0.87 50.10 0.52 11.24 35.96 22.11 -58.12 -53.66 -53.36 -64.78 -36.86 -10.39 24.21 10.66 8.16 6.91 19.07 21.59 21.38 33.39 6.97 -0.65 8.43 -2.43 -4.16 -2.38 -9.63 -5.51 -13.51 -10.11 -13.29 59.45 6.89 57.01 20.91 36.06 -1.81 -5.83 8.99 1.48 -5.15
7 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
8 0.36 -9.61 1.02 -6.04 4.84 -24.33 -8.21 45.78 30.35 38.23 42.16 54.26 -120.54 -115.24 -69.13 -67.13 -70.43 -60.18 5.90 -7.01 15.18 4.81 -33.96 30.18 46.19 57.18 65.44 -41.09 -36.70 -37.47 -29.19 -42.90 -31.67 -4.08 -35.35 -23.70 -17.88 -37.95 -41.20 -50.40 -38.32 -39.40 -70.21 -91.84 -72.54 -80.54 -28.43 25.95 37.78 26.71 38.81 33.30 89.60 58.90 74.10 54.92 69.38 -7.76 -0.12 7.32 3.19 -12.11
18 17 16 15 14 13 12 11 10 9 6.56 6.65 2.17 1.89 2.19 7.63 9.72 3.02 6.06 5.94 -7.93 17.02 -2.08 0.84 8.74 -3.87 -2.08 2.22 -7.67 7.77 -0.36 -3.02 8.47 10.38 -2.20 18.81 24.37 -13.21 -7.41 -1.91 -21.26 -2.55 1.30 6.04 -3.84 9.54 7.06 -3.30 -3.38 -2.67 5.31 -4.77 4.79 0.71 -0.54 11.33 10.86 -1.81 2.19 2.55 -26.34 -0.17 0.57 4.70 6.14 3.40 10.88 -7.20 -12.28 -10.88 -10.43 -1.80 3.35 -3.43 -1.60 2.27 -4.10 -4.56 -5.62 -5.28 -0.10 1.98 5.12 10.58 7.34 8.66 17.18 5.43 66.69 39.60 -13.19 2.59 7.98 5.67 -8.21 -12.86 -8.33 -14.13 34.95 5.52 -2.12 3.61 9.49 4.06 8.03 -11.21 -1.68 0.90 41.30 22.80 0.84 3.16 6.33 1.89 2.89 -3.80 1.16 -0.58 50.69 26.69 18.79 4.48 2.74 -12.77 4.39 0.21 -2.55 5.50 59.82 38.84 -88.49 -3.67 -0.54 -8.49 -5.02 9.67 7.14 -21.67 -178.60 -127.51 -87.67 -9.73 11.83 -4.06 -12.11 -9.84 -14.00 -33.41 -135.46 -85.52 -41.90 -2.76 2.38 2.76 -10.27 -1.73 -12.97 -6.32 -108.76 -70.22 -36.11 -11.89 -4.33 -4.81 2.33 -14.87 -10.11 -17.78 -128.44 -88.00 -48.81 -9.14 5.19 -2.91 2.97 0.22 1.78 -13.40 -97.13 -56.38 -45.05 -2.38 -1.41 1.35 -0.40 1.35 -16.73 -28.13 2.93 29.42 28.30 7.67 11.89 14.52 9.94 -7.08 -17.86 -8.52 38.42 61.66 9.87 10.36 18.72 12.16 2.10 -3.18 -9.11 -12.75 14.32 38.78 38.23 15.11 34.62 25.42 27.02 27.14 11.51 -1.03 11.82 31.32 24.26 21.59 19.85 14.49 25.10 11.68 -2.53 3.47 20.63 27.16 -44.20 3.40 28.79 34.13 1.63 3.17 8.05 26.07 -30.98 -129.14 25.79 2.74 7.53 -5.21 -10.40 -6.23 -7.39 6.02 28.09 10.81 55.69 6.73 7.93 8.61 1.02 3.14 9.37 10.46 45.20 30.51 65.70 22.61 22.01 22.56 19.83 5.24 16.80 28.49 44.74 33.06 69.90 -0.99 14.14 1.65 2.50 -0.47 7.20 4.51 60.30 42.86 16.40 11.02 5.78 5.31 9.06 -28.35 -6.40 -4.72 -64.64 5.09 29.19 7.60 -4.86 -4.86 -0.99 -26.34 -4.06 -8.40 -75.83 -2.43 28.74 1.27 -0.11 -1.61 -3.71 -21.08 2.20 -14.44 -66.48 2.82 40.30 -8.62 -1.56 -9.99 -9.58 -13.90 13.31 -22.82 -62.92 0.88 29.08 -4.93 0.21 3.11 -13.34 -15.74 5.97 -21.83 -62.54 7.74 23.39 1.72 9.28 1.91 -4.18 -24.76 27.71 -16.87 -55.84 12.32 55.72 7.60 8.02 -5.76 -5.53 -29.66 28.43 -9.82 -48.31 14.37 22.70 6.47 16.94 12.11 -3.96 1.27 52.27 -13.85 -56.24 2.95 33.94 5.26 11.41 2.75 -4.56 -17.72 36.14 -13.51 -53.46 9.88 39.55 4.66 8.65 -1.92 -4.86 -27.21 28.07 -13.35 -52.07 13.35 47.49 17.70 36.65 19.65 17.40 9.55 3.77 11.52 24.85 31.12 42.62 10.97 20.93 16.73 14.33 2.81 2.05 14.65 0.92 -1.68 33.67 22.18 19.51 18.83 21.12 12.42 15.05 17.60 12.53 25.87 47.15 12.03 25.29 14.54 11.33 18.10 15.20 1.41 5.19 4.65 -35.19 14.43 4.65 13.30 26.43 5.73 -1.46 24.87 10.06 6.54 -35.46 -0.16 -1.35 -5.30 -5.78 8.33 3.08 -28.65 -127.73 -108.81 -72.32 -11.51 -5.89 4.16 -10.05 14.60 13.46 -25.68 -108.33 -62.11 -57.03 7.19 2.00 1.41 4.54 -25.29 -27.89 -7.08 -102.05 -71.19 -58.05 2.98 6.43 6.76 -5.51 -17.73 -23.46 -14.32 -105.35 -68.65 -1.30 -6.38 0.76 11.02 2.92 7.14 9.94 -15.36 -109.14 -56.21 -32.27 -12.16 -15.19 -10.16 -3.30 -2.92 -9.08 -11.19 -8.70 -9.08 -28.59 9.79 -10.38 -2.86 -4.81 6.43 -7.68 -14.17 -13.41 -14.54 -44.22 -3.02 -0.60 -1.51 4.54 -15.14 -18.87 8.76 -6.32 -18.87 -29.62 1.02 5.45 -2.43 -0.16 4.54 -3.95 -6.27 -6.60 -8.11 -27.13 -0.27 5.79 -2.92 -0.91 3.30 -7.08 4.00 -8.33 -19.46 91.97 15.76 22.04 23.22 15.90 18.88 29.99 5.27 76.50 46.45 40.55 9.25 8.68 12.28 14.59 13.29 17.51 23.39 96.07 61.86 56.68 15.05 6.23 19.73 11.91 4.72 16.31 6.89 53.95 29.27 52.72 10.53 4.77 8.62 7.88 9.75 25.72 18.22 71.95 46.85 60.48 12.65 10.43 15.96 12.57 11.66 22.38 13.44 74.62 46.11 -0.68 2.69 -3.12 -7.06 5.12 1.93 0.21 5.12 -4.06 -3.61 6.78 4.98 4.17 -1.85 -1.20 3.63 -5.41 -0.02 13.12 14.80 14.56 2.57 5.73 -1.25 -3.98 4.95 4.96 -5.45 9.25 10.91 8.78 1.91 -2.81 0.52 -5.97 1.68 5.26 -1.06 11.02 2.72 -5.05 -1.51 -8.59 -5.43 -3.44 -14.18 -6.04 -2.05 -7.13 5.62
19 -3.16 10.12 1.14 -3.87 -3.85 3.40 -0.17 9.96 1.23 0.78 7.08 16.35 -0.76 -5.41 -1.62 -3.83 -3.13 -5.67 7.67 -2.22 23.86 16.40 43.31 2.50 6.56 21.62 -0.14 -17.96 -17.87 -19.94 -30.92 -13.00 -15.32 -3.70 -8.85 -9.29 -9.51 17.51 5.17 9.23 7.41 19.62 -3.19 -0.27 12.54 2.00 10.81 3.46 0.60 -0.75 -0.27 0.71 8.08 7.22 20.77 -0.40 8.92 3.35 -3.49 -8.40 -1.39 -1.49
20 2.38 -7.15 -2.88 -2.78 -0.66 0.35 -2.50 5.92 5.43 -1.03 3.87 5.17 8.70 5.78 -0.32 1.30 3.78 -6.68 2.92 -8.68 19.32 5.52 73.75 -0.09 0.90 5.83 4.34 -41.32 -36.98 -40.56 -51.83 -32.12 -29.31 -17.61 -22.33 -23.08 -23.46 7.41 4.23 0.45 13.81 3.24 8.86 18.11 9.41 8.70 14.75 13.41 7.51 6.49 14.97 15.30 1.89 17.37 27.89 -0.09 11.76 -1.82 3.85 -2.90 1.61 -7.29
21 -0.40 5.45 -4.65 1.06 0.69 0.85 -4.55 2.74 -0.54 7.70 3.28 3.24 -5.41 -4.54 -12.44 -9.56 0.21 -1.91 5.71 -3.89 16.57 6.16 52.49 0.23 7.50 11.54 2.45 -11.40 -5.50 -12.07 -21.35 -10.03 -7.79 5.15 -3.77 -2.14 -1.32 11.07 6.40 5.69 6.91 -9.02 0.05 2.81 -12.59 -2.22 6.05 2.65 -2.43 -4.60 2.00 -2.11 6.28 11.64 21.24 5.45 11.15 0.64 -3.77 -0.97 1.89 4.02
22 3.19 7.67 3.89 -4.16 6.61 0.44 3.09 1.37 -6.72 0.95 1.76 11.44 4.48 -13.13 -8.65 -16.59 -2.06 -5.02 1.77 -5.75 10.85 7.32 7.19 2.12 -2.20 23.69 -2.43 -15.86 -27.16 -21.80 -16.00 -28.18 -66.84 -58.43 -70.16 -65.14 -62.64 19.35 7.84 13.83 13.71 13.84 -2.05 -8.33 -7.35 -8.48 -4.11 -1.46 -0.70 8.60 2.59 -8.06 17.62 -2.43 8.48 0.45 6.03 6.68 -1.44 -7.27 -7.39 2.88
23 0.19 -3.70 20.98 2.10 14.77 9.74 8.07 -21.59 -37.59 -37.87 -27.47 -12.81 1.30 -14.59 -18.49 -22.11 -6.00 -82.24 -58.24 -60.65 -42.54 -53.14 9.75 -7.91 -7.37 6.09 -1.01 -300.32 -318.23 -343.17 -458.06 -296.05 -370.62 -400.73 -382.98 -384.78 -385.68 -0.02 0.82 18.29 10.50 -9.52 22.43 23.03 8.65 13.08 15.40 -6.06 0.00 -11.68 -2.43 10.49 7.88 -3.32 -2.67 -14.66 -3.19 -6.40 -2.38 0.35 -2.86 -5.03
24 3.28 2.10 8.10 1.94 11.33 6.70 6.04 -34.19 -34.47 -28.60 -30.78 -25.84 -3.84 -5.40 -8.81 -9.51 -1.72 -87.32 -68.49 -60.65 -41.91 -63.15 -4.75 -8.33 -10.60 4.96 -1.96 -148.89 -156.56 -169.65 -220.44 -152.69 -106.29 -155.14 -140.29 -133.91 -130.72 -2.55 -2.83 12.55 8.36 -4.54 14.54 19.79 5.08 13.19 16.76 -7.73 -5.08 -8.38 -1.35 -5.35 7.34 -7.92 3.52 -7.03 -1.02 -3.06 -4.34 -0.76 -5.73 2.22
25 -1.86 2.86 -3.35 -11.82 -8.23 -9.23 -5.12 35.94 -20.34 20.88 13.11 15.98 -38.97 -36.11 -34.49 -10.70 -20.21 -8.23 5.05 7.32 15.01 22.38 18.38 2.50 28.13 30.59 29.97 -110.98 -124.03 -117.37 -117.95 -116.51 -144.35 -131.92 -145.91 -140.73 -138.14 17.75 11.44 14.98 14.33 9.25 -29.51 -44.00 -13.57 -33.63 -22.22 -3.30 12.21 -2.87 -7.94 4.76 34.81 34.15 31.84 25.23 31.51 5.05 -2.38 1.01 -2.83 2.43
26 -2.62 -8.94 1.06 -14.23 -13.12 -12.80 -7.05 54.21 -36.46 23.46 13.55 13.00 -97.02 -80.75 -59.89 -63.36 -49.41 -34.36 -13.10 -6.63 -29.88 -7.59 41.13 2.91 34.13 35.06 51.30 -175.82 -192.64 -180.09 -180.10 -171.80 -202.50 -187.35 -200.07 -196.64 -194.93 -2.53 4.35 -5.78 5.36 22.27 -46.06 -64.49 -28.92 -50.22 -41.52 6.71 6.81 -0.27 -0.92 12.22 48.54 49.59 22.09 57.48 44.43 -3.09 -2.43 3.89 1.21 5.00
27 2.03 4.62 -0.09 2.76 -3.52 -2.83 0.34 -13.22 -8.43 -4.82 -8.20 -6.33 -13.68 -10.97 -2.00 -11.46 -6.00 -4.91 -10.92 -7.29 -6.82 -2.88 -5.67 -2.50 0.00 5.12 0.92 18.65 20.03 17.78 16.31 16.12 23.81 19.59 19.94 21.11 21.70 -1.70 0.47 -11.04 -0.28 4.54 -1.19 -3.62 -0.54 0.27 -2.48 -3.46 -2.76 0.22 4.97 -3.94 0.14 -9.37 -8.71 12.58 -1.34 -2.62 1.68 0.52 0.28 -0.33
28 -4.41 -2.80 2.06 1.39 1.91 -4.60 -5.90 8.40 9.89 15.37 11.47 12.20 1.25 -5.40 -4.27 -6.92 -10.76 -30.40 -19.49 -14.98 13.98 21.69 32.74 9.94 13.29 18.59 11.14 21.90 10.15 30.20 30.06 58.69 63.12 135.46 117.24 105.27 99.29 29.19 23.95 24.38 27.75 -2.05 -13.24 -6.65 -24.38 -8.76 -9.95 -2.59 -13.30 -0.16 -4.27 0.92 28.51 10.74 27.40 12.58 19.81 5.38 -0.02 -2.24 -3.12 9.34
32 31 30 29 0.99 3.63 5.17 6.35 -4.25 -1.96 6.70 5.08 0.77 0.97 9.84 14.26 -1.86 -0.94 8.43 13.47 -2.74 -1.61 6.02 7.01 1.70 1.47 9.69 16.12 -8.56 -0.56 6.42 5.33 12.96 3.87 -51.30 -37.57 6.26 2.17 -39.10 -31.05 6.23 6.40 -40.76 -35.30 9.83 5.34 -42.39 -31.83 13.85 8.90 -38.40 -23.41 -3.14 -5.73 14.37 -0.70 -7.14 -3.08 -7.02 -8.81 -3.19 -6.54 4.97 -7.73 -10.32 -4.16 -18.00 -14.11 -8.21 -9.51 16.27 -2.17 14.73 4.11 -198.30 -184.90 11.80 6.68 -153.36 -137.60 3.05 -4.91 -87.20 -77.81 18.76 6.56 -95.32 -92.09 23.23 8.70 -90.74 -86.60 39.60 35.25 -30.54 -7.79 6.23 3.44 -24.40 -7.20 8.75 6.35 -33.20 -18.91 20.70 24.78 -3.87 9.72 22.54 10.26 -29.48 -16.02 8.09 3.11 -142.18 -129.22 -1.68 3.31 -146.91 -146.83 8.39 1.05 -157.82 -151.22 10.95 -4.93 -241.56 -235.75 16.21 2.70 -100.62 -93.08 20.67 -1.96 -37.71 -7.97 58.60 21.50 -30.52 2.27 42.55 3.18 -62.96 -25.25 40.61 7.57 -43.73 -10.32 39.63 9.77 -34.12 -2.85 21.50 16.33 -4.43 3.63 22.45 16.35 4.18 24.78 26.60 12.35 -26.03 -13.17 34.24 18.08 1.55 15.36 4.59 7.95 -7.84 -21.68 -6.43 4.76 31.03 13.84 -17.14 -4.49 55.41 33.30 -23.46 -24.27 13.46 9.30 -13.41 -3.03 5.13 -11.08 -12.22 -4.22 19.19 18.05 -14.32 -12.64 6.43 3.19 1.40 -13.19 8.48 -6.38 -12.21 -5.51 -6.54 -20.33 -0.22 -0.38 4.76 0.48 1.94 -4.64 15.08 3.29 25.84 26.64 15.86 31.57 16.21 15.51 -41.60 -18.72 24.92 23.46 4.20 14.44 18.39 16.95 -37.21 -20.06 21.34 20.64 -14.69 1.81 -1.20 2.69 11.73 8.12 7.38 0.24 10.62 18.17 16.19 6.13 7.08 15.06 3.73 1.04 3.52 8.02 2.39 3.59 11.49 7.36
33 4.27 7.39 2.51 8.42 -0.73 5.57 11.19 -20.25 -8.87 -25.91 -15.35 -6.38 -3.13 -1.83 -2.98 -1.30 5.46 -46.11 -33.63 -22.02 -27.21 -11.23 23.13 5.17 -14.51 15.36 -13.90 -52.34 -59.82 -65.42 -107.99 -41.53 -17.82 13.71 -11.92 -5.34 -2.06 5.61 26.99 -14.65 17.84 -6.22 -1.79 26.33 -14.86 -13.14 3.13 -5.35 -11.30 -14.27 6.05 -5.62 39.34 2.55 -0.07 3.97 11.45 4.49 2.29 3.96 -5.31 -4.25
34 -2.08 -0.40 -0.85 -1.32 -8.33 -8.69 -3.68 11.99 13.24 6.75 15.67 30.70 -64.21 -62.65 -43.68 -27.40 -36.75 4.28 9.65 2.81 -2.43 -14.96 27.75 15.50 15.19 14.06 -3.61 -15.72 -8.97 -10.40 -10.17 -6.73 -5.71 -3.02 -11.84 -6.86 -4.37 -0.35 -8.23 -11.52 -4.51 9.95 -17.19 -15.13 -23.62 -14.21 -31.51 2.38 -2.11 5.14 3.35 8.06 20.29 26.45 15.45 27.63 22.46 0.00 2.31 2.13 0.26 -0.47
35 -6.45 -3.95 -0.49 -5.05 -9.61 -10.46 -5.20 0.94 5.24 -4.72 9.76 37.57 -72.65 -61.89 -43.30 -27.79 -34.21 0.87 13.08 2.39 -2.55 -18.97 52.37 20.65 23.34 20.58 -4.08 -13.57 -3.40 -4.53 -3.07 1.93 -2.52 9.62 0.57 2.56 3.55 16.90 8.45 -2.06 13.57 -1.25 -10.27 -8.75 -29.84 -12.92 -28.86 -10.81 -14.11 -9.46 -5.46 -9.79 17.70 40.78 16.80 30.18 26.37 1.11 7.01 3.10 4.29 1.04
36 -11.05 -3.87 -4.16 -14.54 -18.85 -17.66 -2.78 3.19 20.91 4.27 11.27 16.71 -116.22 -105.57 -77.41 -55.79 -65.08 13.90 27.92 0.62 -3.87 -20.37 101.76 33.06 42.45 49.13 23.76 -25.49 4.18 -4.34 1.46 2.47 -0.62 35.68 4.72 13.26 17.53 33.48 16.47 14.77 29.66 1.78 -22.00 -64.27 -72.59 -37.30 -61.46 -22.11 -52.43 -17.19 -5.40 -19.19 52.43 87.22 39.95 49.81 57.35 7.74 11.94 13.92 3.06 5.78
37 -3.51 10.12 3.33 -1.89 3.90 10.40 0.63 8.07 8.45 -0.52 5.35 5.38 -14.33 -34.05 -5.46 10.16 0.92 -10.64 23.86 13.78 -4.08 29.33 14.94 5.66 12.55 12.11 -39.15 -34.00 -3.56 -38.80 -109.41 -8.21 17.25 26.76 4.86 16.29 22.01 33.04 40.30 37.00 36.65 39.40 29.24 28.00 25.51 26.59 14.06 -6.38 -0.43 -8.76 -45.62 -18.76 0.87 21.68 19.14 17.58 14.82 13.35 2.51 11.06 8.54 15.19
38 -2.15 4.89 10.64 -1.89 -1.96 3.64 7.12 -17.44 0.87 -13.93 -9.97 -9.37 -50.32 -52.37 -16.71 2.97 -11.08 -25.20 0.10 -5.10 -40.47 0.99 43.42 25.14 24.75 27.36 -21.85 -312.31 -330.50 -323.59 -352.47 -299.06 -353.02 -359.43 -369.16 -360.54 -356.23 -18.88 -7.20 -19.84 -8.12 -13.50 64.37 58.05 45.25 63.95 45.52 117.30 81.46 74.06 29.30 53.19 12.84 25.61 27.61 30.33 24.10 7.20 -5.66 22.90 3.31 8.29
39 -16.47 -10.07 -8.00 -14.89 -14.13 -11.35 -9.25 4.86 9.32 1.88 4.67 2.60 -75.79 -71.73 -47.24 -35.62 -42.81 -13.00 8.48 -7.06 -28.96 4.53 12.91 -1.30 10.34 8.97 -26.78 213.21 205.76 309.98 623.36 197.59 397.01 438.53 414.49 416.68 417.77 18.39 33.41 21.80 28.30 27.60 -48.00 -68.97 -65.29 -67.08 -83.36 -75.84 -41.89 -54.98 -19.19 -49.90 -4.46 16.31 18.01 22.40 13.07 -4.11 -14.75 1.04 -0.62 -5.76
40 6.35 4.43 4.32 11.85 7.62 2.64 6.85 -1.09 -13.72 -4.32 -2.18 10.40 -1.46 -4.75 -2.81 -5.89 7.30 -9.61 11.59 5.40 11.75 14.04 0.93 7.81 5.15 20.55 -39.81 8.29 2.52 -2.17 -13.24 -6.27 -2.74 11.23 -6.53 0.65 4.25 10.95 19.92 28.98 26.26 6.20 1.83 -5.40 -5.40 -0.59 3.03 -15.84 -14.43 -7.62 -19.03 -0.59 31.88 1.88 8.26 0.85 10.72 7.64 -1.18 4.91 5.92 7.39
41 6.51 4.88 1.06 12.94 14.18 8.88 2.98 -14.42 -11.04 -18.92 -11.80 -2.83 -0.59 4.22 7.78 14.33 3.41 -25.70 1.41 -13.21 -14.99 -2.19 -3.73 1.42 -1.86 16.30 -41.91 -23.36 -40.73 -37.92 -55.95 -31.65 -36.79 -26.50 -40.66 -34.65 -31.65 1.32 6.39 23.43 27.68 3.28 20.71 13.84 23.51 17.90 6.60 10.60 3.84 1.51 8.27 2.54 45.29 -5.64 -4.79 -6.49 7.09 -2.43 -2.67 11.26 8.35 -5.74
42 -19.00 -10.10 -6.18 -10.59 -18.06 -18.29 -2.69 26.22 24.64 28.51 31.17 45.31 -25.46 -12.11 -3.67 -9.19 -8.97 37.73 28.15 31.90 35.82 48.28 28.57 22.14 25.25 52.69 5.41 72.52 75.96 74.95 82.81 68.51 79.15 99.84 101.08 93.36 89.50 41.95 46.94 60.89 57.00 44.91 -21.25 -27.78 -34.48 -27.25 -21.79 -12.54 -3.57 -8.16 -3.46 -4.59 50.12 24.19 11.40 35.92 30.41 -6.25 -5.61 12.51 2.72 -4.88
43 -2.71 2.08 -5.50 10.27 4.69 -10.47 2.24 -8.78 0.26 6.84 1.75 8.66 -51.95 -83.84 -49.95 -60.16 -64.43 -24.95 5.19 0.82 -8.97 -24.24 155.77 225.44 208.07 223.15 193.69 -8.05 -17.04 -14.01 -16.14 -14.82 -12.67 -7.81 -4.89 -8.46 -10.24 -30.87 -31.41 -16.07 -32.50 64.33 -25.13 -64.38 -16.81 -23.46 -46.06 73.46 60.81 55.89 44.05 66.65 4.15 22.80 22.31 27.98 19.31 1.39 -3.21 -9.67 -8.90 -0.78
44 -13.71 -11.33 -9.01 -0.10 -2.95 -22.54 -6.98 27.61 30.73 31.18 31.43 36.18 -59.62 -93.62 -52.60 -65.51 -69.41 -18.33 19.28 12.51 -6.21 -13.78 130.14 188.11 191.98 202.60 186.13 22.09 18.81 20.47 17.84 23.13 21.41 21.88 30.68 24.66 21.65 -62.91 -73.46 -44.79 -72.38 73.18 -62.92 -102.21 -56.27 -58.38 -103.84 102.05 86.33 76.81 79.35 70.27 19.02 61.55 58.71 60.82 50.03 3.54 5.22 9.08 2.78 4.06
45 3.14 8.04 2.15 12.94 11.04 -7.27 7.04 -14.61 -3.23 3.71 -1.31 8.90 -63.08 -97.95 -58.65 -74.22 -76.17 -31.04 7.22 3.82 -19.63 -30.45 214.60 280.87 286.46 290.41 261.08 -31.13 -46.63 -36.25 -35.99 -31.24 -21.03 -16.97 -10.17 -16.06 -19.00 191.55 187.50 210.12 196.84 346.76 -12.64 -54.82 -11.30 -10.81 -48.38 -161.84 -135.95 -131.52 -139.73 -126.00 15.38 45.76 37.88 45.05 36.02 10.60 7.86 12.51 2.92 7.03
46 2.43 4.17 13.12 1.96 -5.40 -0.78 4.75 -6.70 -11.87 -6.66 -9.62 -13.26 15.35 -13.84 -4.75 -3.57 -2.17 -32.76 -15.03 -21.97 -21.43 -22.84 4.09 22.25 12.56 22.89 9.04 -40.94 -32.38 -36.91 -48.83 -25.48 -16.97 3.45 -25.18 -12.90 -6.76 -22.99 1.65 6.85 15.97 -11.09 23.73 24.27 27.08 27.46 23.52 14.64 22.16 18.81 9.35 21.73 13.22 -16.68 -23.34 0.54 -6.57 4.70 1.53 -5.62 21.60 3.92
47 1.21 0.04 7.38 1.46 -1.01 -3.00 -0.69 1.61 -6.38 -8.12 -5.18 -7.81 19.51 -3.57 5.08 6.27 1.83 -26.00 -15.60 -23.46 -26.99 -14.26 0.57 16.24 6.79 22.25 5.55 -28.50 -27.05 -32.02 -51.51 -21.00 -3.00 6.28 -19.47 -5.40 1.64 -18.15 -4.06 -0.87 12.77 -34.48 22.10 20.37 21.94 11.13 17.35 28.05 42.38 38.00 27.89 27.03 6.40 -20.46 -27.09 5.74 -8.85 -9.82 -5.21 -6.39 12.79 -14.86
48 1.54 -3.02 7.93 2.36 2.57 0.16 -2.12 -10.06 -9.96 -5.57 -8.00 -6.39 -4.71 -23.94 -4.00 -6.70 0.32 -12.41 4.70 -5.22 -6.09 6.40 20.01 29.09 12.69 36.43 14.33 -7.01 -15.65 -14.71 -23.98 -12.20 -1.18 11.99 -14.07 -1.09 5.40 54.11 75.03 77.95 85.90 100.34 2.11 8.60 2.87 8.60 7.84 -46.27 -40.75 -39.41 -38.54 -38.86 45.59 -4.98 -13.02 11.31 9.73 24.66 30.16 28.75 47.91 22.91
49 -12.82 -4.48 -3.40 -0.47 -7.98 -15.48 -8.36 -10.40 -7.69 -1.54 -2.56 9.37 -1.35 -14.71 -0.22 -5.14 -11.19 -55.22 8.24 -1.32 23.18 18.46 14.16 11.87 13.73 23.15 13.62 2.01 -0.38 -7.90 -17.61 -15.63 -4.03 0.00 -1.98 -2.00 -2.02 7.20 22.02 36.03 34.12 38.65 -2.00 -4.22 8.06 4.27 1.03 -3.78 0.38 -9.13 -8.65 -9.79 5.66 22.85 9.01 10.05 11.89 15.58 10.08 -2.43 7.01 9.04
50 -18.08 -9.06 -11.54 -17.89 -16.83 -18.92 -9.68 -4.60 10.62 6.98 7.07 15.27 11.35 -19.19 -11.03 -0.97 -20.87 -27.89 25.37 -3.14 27.26 28.91 52.58 21.97 19.54 24.52 36.60 75.38 81.56 109.14 194.86 84.76 60.27 106.69 74.86 80.61 83.48 30.06 53.45 61.76 75.79 73.78 -16.10 -32.38 12.27 -4.97 -17.68 -22.22 4.70 -27.51 10.81 1.24 36.30 37.47 27.54 14.18 28.87 3.44 7.55 18.50 13.62 -0.75
51 -6.96 -17.65 -11.77 -17.87 -15.91 -24.55 -21.26 -7.48 11.80 5.02 6.85 18.05 29.19 -76.97 -32.64 -35.40 -44.33 -9.25 12.34 -16.33 22.87 28.72 56.45 28.20 66.15 44.86 42.53 43.61 7.79 47.53 86.01 52.72 -1.27 59.82 -12.56 15.33 29.28 13.97 34.53 46.96 45.45 36.97 -60.48 -82.44 -44.59 -70.17 -68.27 -40.38 -15.79 -40.97 -10.64 -17.79 40.85 38.66 33.98 38.40 37.97 22.80 9.47 34.27 35.32 25.46
52 -4.65 6.44 3.82 2.50 4.20 -0.52 3.87 7.77 4.56 -0.52 6.80 15.39 -8.16 -20.54 -3.08 -11.46 2.38 -6.04 14.09 8.31 27.04 20.70 12.81 4.36 14.44 23.13 3.87 9.49 13.41 2.47 -16.31 3.31 -0.99 6.61 -3.31 0.77 2.81 11.00 21.90 23.12 26.67 24.55 -4.71 -11.13 4.33 -6.33 -8.16 -10.22 -8.76 -6.81 -21.67 -2.92 22.96 16.54 11.47 5.03 14.00 13.38 6.58 -4.77 10.10 10.50
54 53 8.75 -4.62 3.42 -4.88 9.37 5.12 -1.56 -6.89 2.22 -2.78 -0.38 -4.98 -1.16 -5.01 17.20 23.60 10.12 0.12 -2.74 4.25 11.36 12.77 20.87 23.10 -3.35 2.87 -4.60 -14.16 4.59 -2.70 -8.54 -4.71 -11.14 -6.64 8.43 15.12 28.43 33.06 12.67 18.55 22.82 13.90 34.90 27.66 10.26 -5.88 14.16 15.00 21.67 10.22 22.65 23.27 19.78 17.67 0.59 20.91 13.90 21.47 13.55 22.91 33.02 36.72 6.71 12.55 6.78 11.42 24.69 45.82 15.17 10.03 15.55 22.42 15.74 28.62 17.65 17.11 38.63 48.15 53.78 74.59 68.74 79.74 50.30 80.20 -13.89 -2.16 -6.38 -4.87 -4.97 -12.97 -6.59 -0.75 -1.35 2.33 -13.78 -8.59 -8.81 -5.19 -6.43 -10.54 -10.49 -9.52 -10.06 -6.82 54.52 66.88 23.03 15.32 27.21 12.60 5.52 14.49 27.57 27.32 6.49 24.78 14.85 21.73 2.33 23.72 -0.07 8.52 3.02 25.96
Table S5. Color Difference Database (11 analytes plus a control).
