Figure 1S. Details of the solvent program used for HPLC separation. 3 1 2 4 5 6 LC DNAP V1 on V2 PAC Detector Mode 4 Time (min) n-C6 (%) DCM (%) IPA (%) Flow (mL/min) Mode 0.00 100 1.5 4 3.00 3 9.50 2 11.00 11.05 95 5 18.00 98 20.00 75 25 23.00 80 20 26.00 10 90 29.00 37.00 3 1 2 4 5 6 V2 on PAC LC DNAP V1 off Detector Mode 3 3 1 2 4 5 6 LC DNAP V1 on Detector V2 off PAC Mode 2 Based on procedures suggested in Robbins, W. K. J. Chromatogr. Sci. 1998, 36, 457-466. Two automated six port valves (Rheodyne, CA, USA) were used to switch solvent flow between two columns. A propylaminocyano (PAC) 250 × 4.6 mm column (Phenomenex, CA, USA) and a dinitroanilinopropyl (DNAP) 250 × 4.6 mm column (ES Industries, Berlin, NJ) containing 5 μm particles with 100 Å pore size and a Phenomenex CN guard column were used.

Figure 2S. Chromatograms of deasphalted ARH and blank Figure 2S. Chromatograms of deasphalted ARH and blank. The dotted boxes indicate the time interval used to collect five fractions, and the fraction number for each fraction is marked on top of each box.

Figure 3S. The time domain signals of five fractions.

I V III IV II III I V II IV I V III II IV I III V II IV III I V II IV Figure 4S. 2-D 1H–13C HSQC-DEPT NMR spectra of the five fractions. Plots show overall peak distribution (left column), and expanded aromatic (middle column) and aliphatic (right column) region. The aliphatic peaks were clustered and assigned as terminal CH3 (I), CH2 in aliphatic group (II), and CH or CH3 in α position (III) and CH2 in α position (IV) of aromatic group. Fraction 1 I V III IV II Fraction 2 V III I II IV Fraction 3 I V III 13C (ppm) II IV Fraction 4 I V III II IV Fraction 5 [ppm] [ppm] [ppm] 20 10 V III I 40 110 20 60 120 30 80 100 IV II 40 130 120 50 140 [ppm] 8 6 4 2 9.0 8.5 8.0 7.5 7.0 6.5 [ppm] 3 2 1 1H (ppm)

Deasphalted ARH fractions Table 1S. Retention time and relative areas of the peaks observed on chromatogram presented in Fig. 1. (Note: Peak # corresponds to the fraction # marked in the Fig. 2). Peak # Deasphalted ARH fractions Retention time (min) Area (%) 1 5.1 18.69 2 9.7 1.32 3 14.9 6.65 4 22.8 16.80 5 29.1 43.15 Table 2S. The relative summed abundance of peaks in each cluster shown in Fig. 5. Cluster number Fraction number 1 2 3 4 5 I 2.8 2.9 3.4 II 94.9 84.7 77.7 81.4 92.0 III 1.0 4.0 3.6 1.6 IV 0.4 2.0 4.3 3.2 1.9 V 0.9 6.4 11.2 8.4 1.1 sum 100 Table 3S. The properties of oil sample used in this study. Abbreviation Sample Name Sample Origin S (ppm) N TAN API ARH Arabian heavy crude oil Saudi Arabia 28,700 1,645 0.29 27.6