S1

Supplementary material

Molecular Mechanisms of Suppressing Asphaltene Aggregation and Flocculation by Dodecylbenzenesulfonic Acid Probed by Molecular Dynamics Simulations

Bin Jiangdagger Rongya ZhangdaggerDagger Na YangdaggerLuhong Zhangdagger Yongli Sundagger Cuiying Jiansect

Lan LiuDagger and Zhenghe XuDagger

daggerSchool of Chemical Engineering and Technology Tianjin University Tianjin

300072 China

DaggerDepartment of Chemical and Material Engineering University of Alberta Edmonton

Alberta Canada T6G 1H9

sectDepartment of Materials Science and Engineering Massachusetts Institute of

Technology 77 Massachusetts Ave Cambridge MA 02139 USA

Corresponding author Department of Chemical and Material Engineering University of Alberta

Edmonton Alberta Canada

E-mail zhengheualbertaca (Zhenghe Xu)

Corresponding author School of Chemical Engineering and Technology Tianjin University

Tianjin 300072 Peoples Republic of China

E-mail address yangnaynatjueducn (Na Yang)

S2

Figure S1 Structure of C5PeC11 and DBSA

Table S1The force field parameters for the substances

Molecule Atom type σnm єkJmol-1

H (-COOH) 0 0O (-OH) 0295 0850C(-COOH) 0358 0277O(-C=O) 0276 1279CH1 0502 0095CH2 0407 0411CH3 0375 0867C 0358 0277N 0357 0293

C5PeC11

H 0237 0118S 0356 1297O(-S=O) 0285 1057O (-OH) 0295 0850H(-SOOOH) 0 0C 0358 0277H 0237 0118CH2 0407 0411

DBSA

CH3 0375 0867CH2 0407 0411

n-heptaneCH3 0375 0867C 0358 0277H 0237 0118TolueneCH3 0375 0867

S3

Table S2 Charges for functional groups of the substances

Functional groups ChargesS1-S6

-(C=O)-OH(from left to right) 0330 -0450 -0288 0408

N and aliphatic carbon connected with N -0200 0200

Ketone carbon and oxygen (C=O) 0450 -0450

Aromatic carbon and hydrogen (C-H) -0140 0140

Aliphatic carbon 0

-C-SO2OH (from left to right) 0160 1043 -0535 -0543 0410

Table S3 Comparison of simulated and experimental properties for toluene and

n-heptane

MoleculeSimulated

density (kgm3)

Experimental density

(kgm3)S7

Simulated RMSD

(times10-9m2s-1)

Experimental RMSD

(times10-9m2s-1) S8S9

Toluene 86560 plusmn01 867 188 plusmn 002 170

n-heptane 68635 plusmn 21 684 342 plusmn 005 310

The average value of the density obtained for the simulated bulk n-heptane and

toluene was 68635 plusmn 21 kgm3 and 86560 plusmn01 kgm3 respectively These values

agreed fairly well with the published experimental results of 684 kgm3 and 867 kgm3

respectivelyS7 Furthermore the simulation predicted the bulk self-diffusivity of these

molecules as (342 plusmn 005) times 10-9 m2s-1 and (188 plusmn 002) times 10-9 m2s-1 respectively

These calculated results were comparable with the reported literature values of 310

times10-9 m2s-1 and 170 times 10-9 m2s-1 respectivelyS8S9

Figure S2 shows the radial distribution functions (RDFs) between polyaromatic

cores of C5PeC11 molecules in different simulation systems It can be seen that after

S4

70 ns the peaks for different time windows overlapped with each other suggesting

the attainment of dynamic equilibrium after 80 ns In addition it can be seen from

Figure S3 that that the values of exhibited an overall decreasing trend at the

beginning corresponding to the aggregation between model compounds in each set of

the simulations These curves reached their final plateau values after a certain time

The plateau values reflected the system reach equilibrium configuration Whatrsquos more

it can be seen from Figure S4 and Figure S5 that the temperature and potential energy

at the end of the MD simulation fluctuated near the equilibrated state These

phenomena cooperated with each other and proved that the simulation cell became

equilibrated before analysis in our research

S5

Figure S2 RDF between polyaromatic cores of C5PeC11 as a function of time in (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S6

Figure S3 Time evolution of during MD simulations for C5PeC11_24

DBSA_48_C5PeC11_24 DBSA_120_C5PeC11_24 C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S3

Table S2 Charges for functional groups of the substances

Functional groups ChargesS1-S6

-(C=O)-OH(from left to right) 0330 -0450 -0288 0408

N and aliphatic carbon connected with N -0200 0200

Ketone carbon and oxygen (C=O) 0450 -0450

Aromatic carbon and hydrogen (C-H) -0140 0140

Aliphatic carbon 0

-C-SO2OH (from left to right) 0160 1043 -0535 -0543 0410

Table S3 Comparison of simulated and experimental properties for toluene and

n-heptane

MoleculeSimulated

density (kgm3)

Experimental density

(kgm3)S7

Simulated RMSD

(times10-9m2s-1)

Experimental RMSD

(times10-9m2s-1) S8S9

Toluene 86560 plusmn01 867 188 plusmn 002 170

n-heptane 68635 plusmn 21 684 342 plusmn 005 310

The average value of the density obtained for the simulated bulk n-heptane and

toluene was 68635 plusmn 21 kgm3 and 86560 plusmn01 kgm3 respectively These values

agreed fairly well with the published experimental results of 684 kgm3 and 867 kgm3

respectivelyS7 Furthermore the simulation predicted the bulk self-diffusivity of these

molecules as (342 plusmn 005) times 10-9 m2s-1 and (188 plusmn 002) times 10-9 m2s-1 respectively

These calculated results were comparable with the reported literature values of 310

times10-9 m2s-1 and 170 times 10-9 m2s-1 respectivelyS8S9

Figure S2 shows the radial distribution functions (RDFs) between polyaromatic

cores of C5PeC11 molecules in different simulation systems It can be seen that after

S4

70 ns the peaks for different time windows overlapped with each other suggesting

the attainment of dynamic equilibrium after 80 ns In addition it can be seen from

Figure S3 that that the values of exhibited an overall decreasing trend at the

beginning corresponding to the aggregation between model compounds in each set of

the simulations These curves reached their final plateau values after a certain time

The plateau values reflected the system reach equilibrium configuration Whatrsquos more

it can be seen from Figure S4 and Figure S5 that the temperature and potential energy

at the end of the MD simulation fluctuated near the equilibrated state These

phenomena cooperated with each other and proved that the simulation cell became

equilibrated before analysis in our research

S5

Figure S2 RDF between polyaromatic cores of C5PeC11 as a function of time in (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S6

Figure S3 Time evolution of during MD simulations for C5PeC11_24

DBSA_48_C5PeC11_24 DBSA_120_C5PeC11_24 C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S4

70 ns the peaks for different time windows overlapped with each other suggesting

the attainment of dynamic equilibrium after 80 ns In addition it can be seen from

Figure S3 that that the values of exhibited an overall decreasing trend at the

beginning corresponding to the aggregation between model compounds in each set of

the simulations These curves reached their final plateau values after a certain time

The plateau values reflected the system reach equilibrium configuration Whatrsquos more

it can be seen from Figure S4 and Figure S5 that the temperature and potential energy

at the end of the MD simulation fluctuated near the equilibrated state These

phenomena cooperated with each other and proved that the simulation cell became

equilibrated before analysis in our research

S5

Figure S2 RDF between polyaromatic cores of C5PeC11 as a function of time in (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S6

Figure S3 Time evolution of during MD simulations for C5PeC11_24

DBSA_48_C5PeC11_24 DBSA_120_C5PeC11_24 C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S5

Figure S2 RDF between polyaromatic cores of C5PeC11 as a function of time in (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S6

Figure S3 Time evolution of during MD simulations for C5PeC11_24

DBSA_48_C5PeC11_24 DBSA_120_C5PeC11_24 C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S6

Figure S3 Time evolution of during MD simulations for C5PeC11_24

DBSA_48_C5PeC11_24 DBSA_120_C5PeC11_24 C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S7

Figure S4 Time evolution of temperature during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S8

Figure S5 Time evolution of potential during MD simulations for (a) C5PeC11_24 (b) DBSA_48_C5PeC11_24 (c) DBSA_120_C5PeC11_24 (d) C5PeC11_24_80ns+120DBSA_80ns and (e) C5PeC11_24_20ns+120DBSA_60ns systems

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S9

Figure S6 Functional groups used in the discussion

Figure S7 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_48_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

Figure S8 Snapshots of C5PeC11 molecules and DBSA molecules taken at different time for DBSA_120_C5PeC11_24 system C5PeC11 molecules were marked in black DBSA molecules were marked in green and solvent molecules were removed for clarity

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S10

Figure S9 Time evolution of RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system

Figure S10 RDFs between C5PeC11 molecules and DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns and C5PeC11_24_20ns+120DBSA_60ns systems averaged over the last 5 ns of MD simulations

Figure S11 RDFs between C5PeC11 molecules and polar group or tail group of DBSA molecules for C5PeC11_24_80ns+120DBSA_80ns system averaged over the last 5 ns of MD simulations

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913

S11

References

(S1) Jian C Tang T Bhattacharjee S Probing the Effect of Side-Chain Length on the Aggregation of a Model Asphaltene Using Molecular Dynamics Simulations Energy Fuels 2013 27 (4) 2057-2067

(S2) Jian C Tang T One-Dimensional Self-Assembly of Polyaromatic Compounds Revealed by Molecular Dynamics Simulations The Journal of Physical Chemistry B 2014 118 (44) 12772-12780

(S3) Jian C Tang T Bhattacharjee S Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene Energy Fuels 2014 28 (6) 3604-3613

(S4) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Probing StructurendashNanoaggregation Relations of Polyaromatic Surfactants A Molecular Dynamics Simulation and Dynamic Light Scattering Study The Journal of Physical Chemistry B 2012 116 (20) 5907-5918

(S5) Teklebrhan R B Ge L Bhattacharjee S Xu Z Sjoumlblom J Initial Partition and Aggregation of Uncharged Polyaromatic Molecules at the OilndashWater Interface A Molecular Dynamics Simulation Study The Journal of Physical Chemistry B 2014 118 (4) 1040-1051

(S6) Teklebrhan R B Jian C Choi P Xu Z Sjoblom J Role of Naphthenic Acids in Controlling Self-Aggregation of a Polyaromatic Compound in Toluene The Journal of Physical Chemistry B 2016 120 (14) 3516-3526

(S7) Riddick J A Bunger W B Sakano T K Organic Solvents Physical Properties and Methods of Purification John Wiley amp Sons New York 1986

(S8) Kondratyuk P Wang Y Liu J Johnson J K Yates J T Inter- and Intratube Self-Diffusion in n-Heptane Adsorbed on Carbon Nanotubes Journal of Physical Chemistry C 2007 111 (12) 4578-4584

(S9) Antalek B Williams A J Texter J Self-diffusion near the percolation threshold in reverse microemulsions Physical Review E 1996 54 (6) R5913