Post on 07-Nov-2020
1
SUPPLEMENTARY INFORMATION
Precision measurement of the growth rate and mechanism of ibuprofen {001}
and {011} as a function of crystallization environment
T. T. H. Nguyen, R. B. Hammond, K. J. Roberts*
Institute of Particle Science and Engineering, Institute of Process Research and Development,
School of Process, Environmental and Materials Engineering, University of Leeds, Leeds, LS2
9JT, Leeds
I. Marziano, G. Nichols
Pfizer Worldwide Research and Development, Sandwich, CT13 9NJ, UK
(*) Corresponding author’s email: K.J.Roberts@leeds.ac.uk
Abstract
The crystallisation of ibuprofen under diffusion-limited conditions measured as a function of
supersaturation, solvent and reactor scale is described in the main paper and in this
supplementary material some additional information is provided. This comprises:
• Details concerning the raw ATR UV/Vis spectra collected and the associated calibration
used to determine the concentration of ibuprofen in 95% ethanol/water, ethyl acetate, and
acetonitrile solvents as a function of temperature (section S1.1)
• Details of the gravimetric calculations used for the determination of the solubility of
ibuprofen in toluene solutions (section S1.2)
• All the raw in-situ microscopy image data and its associated analysis which underpin the
determination of face-specific growth rates as presented in the main paper (section S2).
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2014
2
S1. Data related to solubility determination in 95% ethanol/water, ethyl acetate, and
acetonitrile solvents by ATR UV/Vis spectroscopy
S1. 1 ATR UV/Vis method development
The Beer-Lambert law states that the absorbance of a solution is directly proportional to the
concentration of the absorbing species in the solution and the path length. Hence, ATR UV/Vis
spectroscopy can be employed to determine the concentration of ibuprofen in a solution for a
fixed path length. The calibration curve of ibuprofen was determined by measuring absorbance
versus a range of concentrations using the specific absorbance peak of ibuprofen at 264 nm
(Figure S1).
0
0.02
0.04
0.06
0.08
0.1
0.12
250 260 270 280 290 300
Ab
sorb
ance
Wavelength (nm)
(a)
0.6g/ml0.8g/ml1g/ml1.2g/ml1.4g/ml
0
0.02
0.04
0.06
0.08
250 260 270 280 290 300
Ab
sorb
ance
Wavelength (nm)
(b)
0.4g/ml0.6g/ml0.8g/ml1.0g/ml
3
Figure S1 Spectra of ibuprofen in 95% ethanol/water (a), ethyl acetate (b) and acetonitrile (c)
showing absorbance increase with increasing concentration of solutions and from these
absorbances at 264 nm and known concentrations, calibration curves (d) were obtained.
Table S1 Calibration line of ibuprofen in 95% ethanol/water, ethyl acetate and acetonitrile at
temperature from 15-35oC
Solvents Calibration line
95% Ethanol/Water
Ethyl acetate
Acetonitrile
y = 0.0818x – 0.0172
y = 0.0786x – 0.0034
y = 0.0503x + 0.0017
0
0.005
0.01
0.015
0.02
0.025
250 260 270 280 290 300
Ab
sorb
ance
Wavelength (nm)
(c)
0.1g/ml
0.2g/ml
0.3g/ml
0.4g/ml
0
0.02
0.04
0.06
0.08
0.1
0.12
0 0.4 0.8 1.2
Ab
sorb
ance
Concentration (g/ml)
(d)
AcetonitrileEthyl acetateEthanol
4
Table S1 shows the regression fits obtained from the calibration curves from which the solubility
of ibuprofen in these 3 solvents over the temperature range 15-35oC was determined.
Figure S2 An example of spectra of ibuprofen in ethyl acetate at 15, 20, 25, 30 and 35°C
showing absorbances increase with increasing temperature of saturated solutions and λmax does
not shift with temperature
Spectroscopic exanimation of the ibuprofen solutions in the UV region revealed a strong
absorbance maximum at about 264 nm. The λmax was not found to shift even in different
solvents and concentration nor even as a function of temperature.
The ATR-UV/Vis spectroscopy calibration shows a linear correlation between UV/Vis
absorbance intensity and the solute concentration for different concentrations of ibuprofen in
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
250 255 260 265 270 275 280 285 290 295 300
Ab
sorb
ance
Wavelength (nm)
5
solvents. For a constant solution concentration, absorbance was found to be quite constant as a
function of a temperature, as shown in Figure S2.
S1.2 Data related to solubility determination toluene solvents by gravimetric
methods
Table S2 provides the raw gravimetric data together with the associated determination of the
solubility of ibuprofen in toluene solutions over the temperature range from 15-35°C was
determined.
Table S2 Solubility of ibuprofen in toluene solutions over the temperature range from 15-35°C
T(°C) 15 20 25 30 35
Sample 1 0.367 0.46 0.588 0.75 0.913
Sample 2 0.366 0.46 0.591 0.753 0.974
Sample 3 0.588 0.936
C(g/g) 0.367 0.46 0.589 0.7515 0.941
STDEV 0.00173 0.00212 0.03080
6
S2. Crystal growth rate measurement in the 0.5ml cuvette cell and the 15ml
jacketed vessel
The data presented comprises plots of growth rate versus time for the {011} and {001} faces for
all the crystals measured together with a representative image set for one of these crystals.
S2.1 Data from the 0.5ml cuvette cell
S2.1.1 95% Ethanol/Water Solutions
σ = 1.15
y = 21.7x + 213.5y = 22.5x + 232.67
y = 19.3x + 347.4
y = 22.6x + 274.7
y = 21.7x + 142.9
0
100
200
300
400
500
0 2 4 6 8 10
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 1.15
y = 12.2x + 130.35
y = 14.3x + 130.33
y = 10.9x + 205.7y = 14.8x + 173
y = 14.1x + 98.65
0
100
200
300
0 2 4 6 8 10
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.15
7
σ = 0.89
σ = 0.79
y = 14.0x + 182.9
y = 12.5x + 152.4y = 14.5x + 157.7
y = 16.1x + 404.57
0
200
400
600
800
0 5 10 15 20 25
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.89
y = 5.7x + 93.9
y = 5.8x + 78.6y = 5.9x + 83.8
y = 7.4x + 191.2
0
100
200
300
400
0 5 10 15 20 25
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.89
y = 13.5x + 156.8
y = 9.5x + 151.6
y = 12.5x + 529.4
y = 10.7x + 237.1
y = 11.2x + 199.4
0
200
400
600
800
0 10 20 30 40
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.79
y = 4.9x + 79.2
y = 4.4x + 71.2
y = 5.1x + 295.4
y = 4.3x + 98.4
y = 4.1x + 90.4
0
100
200
300
400
500
0 10 20 30 40
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 0.79
8
σ = 0.66
S2.1.2 Ethyl Acetate Solutions
σ = 1.12
y = 11.2x + 80.9
y = 10.3x + 82.6
y = 6.9x + 188.6
y = 7.6x + 459.9
y = 6.6x + 379.8
0
100
200
300
400
500
600
700
0 5 10 15 20 25
Dis
tan
ce f
rom
cen
ter
to f
aces
(μ
m)
Time (mins)
The {011} face at σ = 0.66
y = 4.4x + 124.0
y = 2.5x + 85.2
y = 4.0x + 35.6y = 3.6x + 33.1
y = 3.5x + 103.6
0
50
100
150
200
250
0 5 10 15 20 25
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 0.66
y = 66.5x + 270.5y = 60x + 198.8
y = 72.2x + 342.4
y = 62.8x + 310.8
y = 55.3x + 428.4
y = 50.9x + 289.6
0
200
400
600
800
0 1 2 3 4 5 6
Dis
ntan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 1.22
y = 9.7x + 62.5
y = 10.8x + 66.3
y = 9.3x + 67.5y = 15.4x + 74.9
y = 14.7x + 74.15
y = 13.2x + 52.2
0
40
80
120
160
200
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.22
9
σ = 1.06
σ = 0.97
y = 63x + 481.67
y = 47.7x + 351.8
y = 55.4x + 456.4
y = 47.6x + 147.8
y = 48.1x + 555.1
y = 48.7x + 401.4
y = 56.7x + 251.5
0
100
200
300
400
500
600
700
800
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.06
y = 9.3x + 43.75
y = 10x + 79.167 y = 9.8x + 74
y = 10.4x + 79.3
y = 9.9x + 25.4
y = 8.9x + 78.5
y = 9.6x + 41.75
0
20
40
60
80
100
120
140
0 1 2 3 4 5 6
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} at σ = 1.06
y = 54.6x + 201.1
y = 47.6x + 594.7
y = 47.7x + 725.9
y = 52.1x + 171
y = 45.1x + 111.5y = 46x + 122
0
200
400
600
800
1000
1200
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face in at σ = 0.97
y = 8.7x + 37.55
y = 9.5x + 116.65
y = 8.4x + 34.8
y = 7.4x + 20.917y = 7.3x + 24.333
0
50
100
150
200
0 2 4 6 8
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 0.97
10
σ = 0.85
σ = 0.76
y = 39.1x + 159.49
y = 41.8x + 551.9
y = 37.9x + 1049.3
y = 42x + 631.5y = 48.7x + 243.76
y = 43.5x + 143.17
y = 43.1x + 642.62
y = 43.9x + 415.4
0
200
400
600
800
1000
1200
1400
0 5 10 15
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.85
y = 5.9x + 26.206
y = 5.7x + 72.2
y = 6.6x + 72.95
y = 6.8x + 46.952
y = 6x + 22.667
y = 6.5x + 70.7
0
40
80
120
160
200
0 5 10 15
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.85
y = 42.8x + 174.6
y = 34.5x + 372.5y = 37.6x + 323.5
y = 36.3x + 396.6
y = 34.7x + 757.6
y = 38.9x + 238.59
0
200
400
600
800
1000
1200
1400
0 5 10 15 20
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.76
y = 4.8x + 29
y = 4.2x + 61.85 y = 4.1x + 48.167
y = 4.8x + 58.2
y = 3.3x + 87.45
y = 5.0x + 34.008
0
20
40
60
80
100
120
140
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.76
11
σ = 0.69
σ = 0.54
y = 29.3x + 315.9y = 31.4x + 232
y = 30.8x + 292
y = 31.6x + 237.2
y = 33.6x + 143.5
0
400
800
1200
1600
0 10 20 30 40
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.69
y = 3.3x + 36.8y = 4.2x + 27.3
y = 3.4x + 30.8
y = 3.2x + 22y = 3.2x + 22.9
0
40
80
120
160
0 10 20 30 40
Dis
tanc
e fr
om c
ente
r to
fac
es (μ
m)
Time (mins)
The {001} face at σ = 0.69
y = 18.9x + 293.5
y = 16.6x + 310.1
y = 20.7x + 175.4
y = 16.0x + 176.9
y = 15.9x + 652.6
0
400
800
1200
0 5 10 15 20 25 30
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.54
y = 2.2x + 36.839
y = 1.6x + 30
y = 1.9x + 18.81
y = 1.7x + 22.3
y = 1.4x + 70.833
0
40
80
120
0 5 10 15 20 25 30
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.54
12
S2.1.3 Acetonitrile Solutions
σ = 1.31
σ = 1.12
y = 109.2x + 511.17
y = 113.4x + 711.4
y = 103.9x + 320.4
y = 110x + 436.5
y = 99.5x + 418.17
y = 136x + 589
0
200
400
600
800
1000
1200
0 1 2 3 4 5
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} at σ = 1.31
y = 13.4x + 83.75
y = 17.3x + 102.05
y = 16.1x + 35.55
y = 12.5x + 75.667y = 17.3x + 58.3
0
40
80
120
160
200
0 1 2 3 4 5
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 1.31
y = 90.4x + 554
y = 99.6x + 267.19
y = 94x + 606.67
y = 96.5x + 154.4
y = 93.5x + 501.6
y = 80.5x + 536.71
0
200
400
600
800
1000
1200
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.12
y = 10.5x + 51.5 y = 13x + 36
y = 10.5x + 75.5y = 11.8x + 81.571
y = 7.9x + 33.8
0
20
40
60
80
100
120
140
160
0 1 2 3 4 5 6Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.12
13
σ = 1.03
σ = 0.93
y = 77.0x + 209.9
y = 70.2x + 839.2y = 98.4x + 841.9
y = 67.7x + 416.17
y = 88.2x + 830.83y = 77.8x + 1033.3
0
200
400
600
800
1000
1200
1400
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.03
y = 7.7x + 21.6
y = 10.7x + 73.9
y = 5.9x + 51.4
y = 6.3x + 58.833y = 6.3x + 84.05
0
20
40
60
80
100
120
0 2 4 6 8
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 1.03
y = 71x + 839.67
y = 55.7x + 263.4y = 55.7x + 263.4
y = 61.3x + 855.3
y = 55.5x + 369.5
0
200
400
600
800
1000
1200
1400
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.93
y = 5.5x + 57.667
y = 4.8x + 35.35
y = 4.6x + 38.85
y = 5.1x + 100.1
y = 4.9x + 33.15
0
20
40
60
80
100
120
140
0 1 2 3 4 5 6
Dis
tan
t fr
om c
net
er t
o fa
ce (μ
m)
Time (mins)
The {001} face at σ = 0.93
14
σ = 0.79
S2.1.4 Toluene Solutions
σ = 0.86
y = 49.8x + 326.4
y = 48x + 329.8
y = 48.7x + 329.2
y = 60.5x + 282.76
y = 50.3x + 220.81
0
200
400
600
800
1000
0 2 4 6 8 10 12
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.79
y = 4.8x + 18.2
y = 3.4x + 40.3
y = 3.3x + 37.2y = 3.2x + 39.3
y = 3.7x + 24.381
y = 2.9x + 16.19
0
20
40
60
80
0 2 4 6 8 10 12
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {001} face at σ = 0.79
y = 38.9x + 351.8
y = 37.4x + 354.7
y = 38.5x + 354.0
y = 29.2x + 581.4
y = 29.7x + 211.3
y = 32.6x + 1041.6
0
200
400
600
800
1000
1200
1400
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.86
y = 3.3x + 37.0
y = 3.0x + 35.1
y = 3.1x + 35.8
y = 2.0x + 15.2
y = 3.1x + 79.4
y = 3.4x + 74.1
0
20
40
60
80
100
120
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.86
15
σ = 0.78
σ = 0.70
y = 27.5x + 629.9
y = 31x + 239.6
y = 34.4x + 317.1y = 30.5x + 524.6
y = 29.0x + 509.3
0
200
400
600
800
1000
1200
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.78
y = 2.1x + 45.9
y = 2.4x + 22
y = 2.5x + 23.2y = 2.2x + 36.4
y = 2.2x + 43
0
20
40
60
80
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.78
y = 28.9x + 534.6
y = 25.6x + 427.3
y = 27x + 205.6
y = 30.8x + 438.6y = 26.4x + 400.4
y = 28.9x + 306.2
0
400
800
1200
1600
0 5 10 15 20 25 30
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.7
y = 2.0x + 25.9
y = 1.7x + 22.8
y = 1.9x + 29.9
y = 1.5x + 56.9
y = 2.0x + 23
0
20
40
60
80
100
0 5 10 15 20 25 30
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.7
16
S2.2 Data from the 15ml jacketed vessel
S2.2.1 95% Ethanol /Water Solutions
σ = 1.15
σ = 0.97
y = 22.1x + 163
y = 25.6x + 198.8
y = 22.4x + 155
y = 31.5x + 186.4y = 21.6x + 272.8
0
100
200
300
400
500
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.15
y = 12.9x + 113
y = 14.4x + 119.5
y = 12.6x + 98.7
y = 12.8x + 125.7
y = 13.4x + 158.2
0
50
100
150
200
250
300
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r fa
ce (μ
m)
Time (mins)
The {001} face at σ = 1.15
y = 22.5x + 174y = 25.8x + 146.8
y = 27x + 157.33
y = 26.6x + 280.7
y = 20.9x + 289.8
y = 25.5x + 246.3y = 28.3x + 238.2
0
100
200
300
400
500
0 2 4 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.97
y = 17.8x + 341.5
y = 14x + 112.7y = 14.8x + 99.2
y = 16x + 103.3
y = 13.3x + 186.5
y = 15.8x + 149.8
0
100
200
300
400
500
0 2 4 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.97
17
σ = 0.89
σ = 0.66
y = 16.6x + 335.4
y = 16.9x + 592.6
y = 16.1x + 182.9
y = 16.4x + 426
y = 18.3x + 609.4
0
200
400
600
800
1000
0 2 4 6 8 10 12Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.89
y = 8.1x + 157.3
y = 6.2x + 234.1
y = 7.2x + 95.9
y = 6.6x + 214.5
y = 7.9x + 310.46
0
100
200
300
400
500
0 2 4 6 8 10 12
Dis
tanc
e fr
om c
net
er t
o fa
ce (μ
m)
Time (mins)
The {001} face at σ = 0.89
y = 11.3x + 232.33
y = 12.2x + 204.47
y = 10.3x + 617.8
y = 9.9x + 358.57
y = 11.7x + 336.4
0
200
400
600
800
1000
0 5 10 15 20 25 30
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.66
y = 3.4x + 78
y = 4.2x + 74.731
y = 4.2x + 226.8
y = 3.6x + 156.43y = 4.5x + 156.4
0
100
200
300
400
0 5 10 15 20 25 30
Dis
tan
ce f
rom
cen
ter
face
(μ
m)
Time (mins)
The {001} face at σ = 0.66
18
S2.2.2 Ethyl Acetate Solutions
σ = 1.22
σ = 1.06
y = 67.3x + 422.1y = 59.5x + 416.4
y = 68.5x + 397.67y = 65.2x + 355.4
y = 70.6x + 644.6
y = 63.5x + 379y = 67.1x + 337.8
y = 61.7x + 388.8
0
200
400
600
800
1000
0 1 2 3 4 5 6 7 8
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 1.22
y = 15.8x + 97.6
y = 13.6x + 86.2
y = 12.3x + 89.2y = 12.7x + 88.2
y = 13.7x + 96.5y = 15.3x + 90.0
y = 14.1x + 76.4
y = 13.2x + 90.8
0
50
100
150
200
250
0 1 2 3 4 5 6 7 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.22
y = 53.8x + 499
y = 58.6x + 241.1y = 56.5x + 254.5
y = 59.1x + 231.7
y = 58.1x + 133
y = 62.1x + 207.8
y = 62.3x + 245.1
0
200
400
600
800
1000
0 1 2 3 4 5 6 7 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.06
y = 12.4x + 114.1
y = 12.7x + 56.9
y = 12.9x + 57.4 y = 12.9x + 56.5
y = 13.0x + 59.6
y = 12.2x + 52.6
y = 11.8x + 52.8
0
50
100
150
200
0 1 2 3 4 5 6 7 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.06
19
σ = 0.97
σ = 0.85
y = 54.3x + 283.8
y = 52.1x + 402.1
y = 51.3x + 582.3y = 50.1x + 508.6
y = 55.3x + 558.1
y = 55.1x + 220.8
0
200
400
600
800
1000
0 1 2 3 4 5 6 7 8
Dis
tan
ce f
rom
cen
ter
to f
ace
(μ
m)
Time (mins)
The {011} face at σ = 0.97
y = 10.8x + 55.7
y = 10.1x + 78.4
y = 9.4x + 113.4
y = 11.4x + 102.7y = 9.2x + 113.4
y = 9.8x + 48.2
0
40
80
120
160
200
0 1 2 3 4 5 6 7 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.97
y = 51.9x + 464.2y = 51.8x + 447.5
y = 41.3x + 245.1y = 46x + 255.3
y = 46.2x + 268.3y = 44.9x + 280.8
0
200
400
600
800
0 1 2 3 4 5 6 7 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.85
y = 7.1x + 75.1
y = 5.8x + 37.8
y = 6.9x + 35.8
y = 5.3x + 31.1
y = 6x + 51
0
20
40
60
80
100
120
0 1 2 3 4 5 6 7
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.85
20
σ = 0.76
σ = 0.69
y = 44.2x + 328.6
y = 39.7x + 241.1y = 43.7x + 475.2
y = 41.7x + 434.8
y = 39x + 410.3
0
200
400
600
800
1000
1200
0 4 8 12 16
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.76
y = 6.1x + 50.6
y = 5.1x + 34.9
y = 5.8x + 70.55
y = 6.1x + 69.1y = 5.9x + 56.917
0
50
100
150
0 4 8 12 16
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.76
y = 33.3x + 475.8y = 40.3x + 450.17
y = 38.1x + 338.2y = 38.76x + 328.8
y = 36.6x + 484y = 37.3x + 498.5
y = 31.84x + 246.2
0
200
400
600
800
1000
1200
0 5 10 15 20
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.69
y = 4.4x + 49.3
y = 4.32x + 40
y = 4.4x + 55.3
y = 2.5x + 25.5
0
20
40
60
80
100
120
140
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.69
21
σ = 0.54
S2.2.3 Acetonitrile Solutions
σ = 1.31
y = 20.3x + 329.6
y = 18.6x + 254.4
y = 24.8x + 625.2
y = 16.6x + 480.2y = 15.4x + 429.6
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25
Dis
tanc
e fr
om c
ente
r to
fac
e(μ
m)
Time (mins)
The {011} face at σ = 0.54
y = 2.2x + 30.5
y = 1.8x + 24
y = 1.5x + 41.6
y = 1.9x + 51y = 1.9x + 47.2
0
20
40
60
80
100
0 5 10 15 20 25
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.54
y = 101.3x + 434.6
y = 121.5x + 473.8y = 115.5x + 614
y = 137.7x + 630.7
y = 120x + 275y = 103x + 283
y = 126x + 454
y = 141.9x + 249.2
y = 128.7x + 271.4
y = 115.2x + 258.8
y = 129x + 263.3
200
400
600
800
1000
1200
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.31
y = 17.9x + 77.8 y = 18x + 93
y = 14.5x + 42.2
y = 18.3x + 50.5
y = 16.5x + 62.8
y = 16.0x + 51.0
0
20
40
60
80
100
120
140
160
0 1 2 3 4 5 6
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.31
22
σ = 1.12
σ = 1.03
y = 103.5x + 260.2
y = 108.7x + 252.2
y = 102.5x + 263
y = 117x + 527.6
y = 93.0x + 209.7
0
200
400
600
800
0 1 2 3 4
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} at σ = 1.12
y = 12.9x + 37.5y = 13.4x + 38.7
y = 12.5x + 39.9
y = 13.8x + 81.3
y = 10.8x + 24.5
0
20
40
60
80
100
120
0 1 2 3 4
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.12
y = 83.1x + 526.7
y = 86.2x + 424.4
y = 74.6x + 470.6
y = 78.8x + 344.5
y = 84.8x + 442.5
y = 98.7x + 312.9
y = 91.6x + 301.9
0
200
400
600
800
1000
0 1 2 3 4 5 6 7
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.03
y = 9.5x + 64.1y = 9.9x + 45.4
y = 9.2x + 48.9
y = 8.1x + 35.6
y = 9.8x + 49.5 y = 9.3x + 33.4
y = 10.2x + 38.1
0
20
40
60
80
100
120
0 1 2 3 4 5 6 7
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.03
23
σ = 0.93
σ = 0.75
y = 77.7x + 438.2
y = 70.4x + 326.4
y = 70.7x + 657.1
y = 75.6x + 300.6
y = 70.2x + 323.2
0
200
400
600
800
1000
1200
0 1 2 3 4 5 6 7
Dis
tan
ce f
rom
cen
ter
to f
ace
(μm
)
Time (mins)
The {011} face at σ = 0.93
y = 6.3x + 36.7
y = 5.7x + 25.2
y = 5.9x + 44.6
y = 5.6x + 22.4
y = 5.6x + 24.3
0
20
40
60
80
0 1 2 3 4 5 6 7
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.93
y = 47.5x + 859
y = 57.5x + 342.6
y = 61x + 266.3
y = 62.2x + 316.6y = 60.3x + 392.2
y = 51.8x + 246.2
y = 55.9x + 254.3
y = 54x + 375.5
0
200
400
600
800
1000
1200
0 2 4 6 8 10
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.75
y = 2.875x + 40.417
y = 5.7x + 27.143
y = 5.35x + 25.45y = 5.5x + 36
y = 5x + 25.833
y = 5.425x + 25.6y = 4.65x + 24.3
0
20
40
60
80
100
0 2 4 6 8 10
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.75
24
S2.2.4 Toluene Solutions
σ = 1.17
σ = 0.86
y = 46.6x + 360.1
y = 46x + 255.3
y = 41x + 215
y = 43.1x + 186.8
y = 42.3x + 443.2
0
100
200
300
400
500
600
700
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 1.17
y = 4.4x + 36.2y = 5.3x + 35
y = 5.1x + 29.8
y = 5.5x + 27.9y = 4.8x + 54.6
0
20
40
60
80
0 2 4 6 8
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 1.17
y = 40.1x + 386.5
y = 40.1x + 386.51
y = 36.6x + 483.6
y = 43.3x + 265.9
y = 37.4x + 239.4
y = 34.5x + 598.1
0
200
400
600
800
1000
0 2 4 6 8 10
Dis
tanc
e fo
rm c
ente
r to
fac
e (μ
m)
Time (mins)
The {011} face at σ = 0.86
y = 3.4x + 38.2
y = 4.4x + 48.9
y = 2.3x + 43.4
y = 4.5x + 32.4
y = 3.2x + 26.9
y = 3.3x + 57
0
20
40
60
80
100
0 2 4 6 8 10
Dis
tanc
e fr
om c
ente
r to
fac
e (μ
m)
Time (mins)
The {001} face at σ = 0.86
25
σ = 0.78
σ = 0.70
y = 34.7x + 625.8
y = 38.6x + 659.1
y = 27.9x + 641.7
y = 37.4x + 335.4y = 34.5x + 334.2
y = 28.7x + 217
0
200
400
600
800
1000
1200
1400
0 5 10 15 20
Dis
tan
ce f
rom
cen
ter
to f
ace
(µm
)
Time (mins)
The {011} face at σ = 0.78
y = 3.1x + 46.1
y = 2.9x + 46.6
y = 2.9x + 20.3
y = 2.2x + 35.4
0
20
40
60
80
100
120
0 5 10 15 20
Dis
tanc
e fr
om c
ente
r to
fac
e (µ
m)
Time (mins)
The {001} face at σ = 0.78
y = 29.1x + 501.8
y = 32.9x + 610.6
y = 31.4x + 313.2
y = 31.4x + 541.6
y = 35.4x + 838.2
0
200
400
600
800
1000
1200
0 2 4 6 8 10 12
Dis
tanc
e fr
om c
ente
r to
fac
e (µ
m)
Time (mins)
The {011} face at σ = 0.7
y = 2.2x + 34.2
y = 2.9x + 46.6
y = 2.0x + 26.5
y = 2.9x + 37.5y = 1.9x + 51.8
0
10
20
30
40
50
60
70
80
0 2 4 6 8 10
Dis
tanc
e fr
om c
ente
r to
fac
e (µ
m)
Time (mins)
The {001} face at σ = 0.7