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SYNTHESIS,CHARACTERIZATION AND MOLECULAR DYNAMIC
SOLVENTS
BY
SAMPSON ASARE
Doctor of Philosophy
Major in Chemistry
2018
iii
ACKNOWLEDGEMENTS
CONTENT
LIST OF ABBREVIATIONS......................................xv
1.0 INTRODUCTION........................................ 1
1.2.1 Definition........................................11
2.0.Introduction.........................................48
2.2 Methodology...................................... . 31
2.2.1 Materials.........................................31
3.1.2 pH ................................................52
3.1.5 Viscosity.........................................53
3.2.3 Viscosity.........................................57
4.4 Conclusion..........................................119
REFERENCE .................................................127
x
LIST OF FIGURES
LIST OF TABLES
LIST OF EQUATIONS
LIST OF ABBREVIATIONS
π*-----------------------Dipolarity/polarizability parameter
ChCl----------------------------Choline Chloride
H2O -----------------------------Water
Mg ------------------------------milligram
μL ------------------------------microliter
oC ------------------------------Degree centigrade
% -------------------------------Percentage
Cm ------------------------------centimeter
Etc.-----------------------------Et cetera
g ---------------------------- gram
Kg --------------------------- Kilogram
Kcal --------------------------kilocalories
M ------------------------------Molar
kJ ------------------------------kilojoules
Mg ------------------------------milligram
MHz -----------------------------Megahertz
mL ------------------------------milliliter
Pa ------------------------------ Pascal
Wt ---------------------- Weight
s --------------------------- Second
ρ --------------------------- Density
ABSTRACT
SOLVENTS
SAMPSON ASARE
2018
the binary DESs have been formulated with water as the sole
the sole HBD in the formulation of type III DES and to exploit
formulated.
DES formation from the choline chloride and water. The largest
of -82.9oC.
CHAPTER ONE
INTRODUCTION
through the work of Paul Anastas and John Warner when they
promote sustainability.
Number Principle
1 Prevent waste
2 Maximize atom economy
3 Less hazardous chemical syntheses
4 Safer chemicals and products
5 Safer solvents and reaction conditions
6 Increase energy efficiency
7 Use renewable feedstocks
8 Avoid chemical derivatives
9 Use catalysts
Design chemicals and products to degrade
10
after use
11 Realtime analyses to prevent pollution
12 Minimize potential for accidents
solvents are the most often used and, thus, generate the most
reclamation.
impacts have not been the only driving factors toward the
popular.
1.1 JUSTIFICATION
mental retardation.
ions (cation and anion) which when combined form liquids. The
temperature.
systems.
9
The third type of DES has been the most prominent solvents
QAS?
10
simulations.
1.2.1 Definition
mixture. These DESs are distinct from ionic liquids (IL) which
cation.
12
the mixture.
formula Cat+X-zY.16
phosphonium or sulfonium.
Y molecules.
13
1.2.2 Classification
halide and M includes Fe, Zn, Sn, Al, Ga, and In. Examples of
include the following metals Cr, Co, Cu, Ni, and Fe. The
choline chloride.
hexanediol28.
organisms31-32.
the production of heat shock proteins (small hsp, hsp 70, and
cryogenic organisms.
idea of existence44-49.
1.2.5 WATER
Though very small in size (2.75 A), it has two hydrogen bond
atom economy16, 56 .
21
This is the major reason for the high cost of ionic liquids.
DESs shows that ILs are less green than DESs57. Again, recent
HBAs and HBDs that are generally less toxic. Also, DESs
toxicity and high cost. For instance, data from Web of Science
Number of Publications
450
400
350
300
250
200
150
100
50
0
2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017
Years
five years.
Number of Publications
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
1994
1997
2000
2003
2010
2013
2016
1992
1993
1995
1996
1998
1999
2001
2002
2004
2005
2006
2007
2008
2009
2011
2012
2014
2015
2017
Years
Figure 1.4. Number of publications containing the phrase
DESs and ILs research. In both DESs and ILs, synthesis and
Together, the two fields account for 26% and 30% of areas or
Analysis Property
14% 26%
Nanoparticles
8%
properties of DES
26
*Nanotechnology
Preparation
Biological 0%
6% Electrochemistry 3%
3%
Synthesis
Separation
20%
13%
Analysis
17%
Property
28%
Nanoparticles
10%
and DESs
27
based polymers69.
been applied, enzyme kinetics and activity have been the focus
complex polymers85.
CHAPTER TWO
FORMULATION AND SPECTROSCOPIC ANALYSIS OF DEEP EUTECTIC
SOLVENT
2.0 INTRODUCTION
200215. Abbot and his colleagues found that a 1:2 molar ratio
synthesis of the first type III DES by Abbot et al. 2002. The
freeze-drying.
2.2 METHODOLOGY
2.2.1 MATERIALS
(Waltham, MA) was used to obtain FTIR spectra of all the DESs
1800; range: 300 nm – 1000 nm; and time = 5s. The spectra
Proton NMR(H1-NMR) spectra were obtained for all the DESs and
the DESs. The D2O were used directly. In the case of DMSO-d6,
1
0.9
WATER
0.8
0.7
0.6
0.5
Transmittance
0.4
0.3
0.2
1638 0.264
0.1
694.4
0.272
0
-0.1
3445 0.001
3320 0.001
-0.2
-0.3
-0.4
-0.5
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400
Wavenumbers [1/cm]
water (below). The -OH peak in the choline chloride and water
(1:10).
2.0, 2.1, and 2.2). This coupled with the band broadening
within the lower molar ratios of the ChCl and H 2O with the
H2O.
38
(blue), 1:3 (cyan), and 1:4 (black). The -OH band area
the band in the solid ChCl. The pure water molecule (HBD)
DESs using NMR. NMR studies suggest the protons around the
DES δ/ppm
hydrogen bonding. The shifts for the native -OH group in the
CH3
H3C +
N
H3C
OH
3.10.
42
0.35
0.30
0.25
0.20
0.15
0.10
0.05
-0.05
-0.10
-0.15
-0.20
-0.25
-0.30
-0.35
-0.40
2.0
Figure 2.4. NMR of all choline Cl:water DESs. From bottom,
1:5, 1:6, 1:8, and 1:10.
1.5
1.0
0.5
Choline Chloride
6000
5000 A
4000
Intensity
3000
2000
1000
200 300 400 500 600 700 800 900 1000 1100
Wavenumber(cm-1)
ChCl:H2O(1:1) 1400
ChCl:H2O(1:2)
3000
2500
B 1200
1000
C
2000
Intensity
1000 600
500 400
0 200
200 300 400 500 600 700 800 900 1000 1100 200 300 400 500 600 700 800 900 1000 1100
Wavenumber(cm-1) Wavenumber(cm-1)
1400 ChCl:H2O(1:4)
D ChCl:H2O(1:3) 1400
1200
1200
E
1000
1000
Intensity
Intensity
800
800
600
600
400 400
200 200
200 300 400 500 600 700 800 900 1000 1100 200 300 400 500 600 700 800 900 1000 1100
Wavenumber(cm-1) Wavenumber(cm-1)
2500
F ChCl:H2O(1:5)
ChCl:H2O(1:6)
1800
G
2000 1600
1400
Intensity
1500 1200
Intensity
1000
1000
800
600
500
400
200
0
200 300 400 500 600 700 800 900 1000 1100 200 300 400 500 600 700 800 900 1000 1100
Wavenumber(cm-1) Wavenumber(cm-1)
ChCl:H2O(1:10)
1400
1800
ChCl:H2O(1:8)
1600
H 1200
I
1400
1000
Intensity
1200
Intensity
800
1000
800 600
600
400
400
200
200
200 300 400 500 600 700 800 900 1000 1100 200 300 400 500 600 700 800 900 1000 1100
Wavenumber(cm-1) Wavenumber(cm-1)
6000
J
Raman Intensity
4000
2000
chlorides DESs.
-60
Freezing point (oC)
-65
-70
-75
-80
-85
50 60 70 80 90
Molar Fraction of water in DES(%)
DESs16,55.
48
60
50
y = 256.51x2 - 239.04x + 72.571
R² = 0.9893
40
WATER (%)
30
20
10
0
0 0.1 0.2 0.3 0.4 0.5 0.6
2.4 CONCLUSION
and water as solely the HBD with 100% atom economy. The
CHAPTER THREE
temperature.
3.1.0 DENSITY
separations.
51
3.1.1 CONDUCTIVITY
3.1.2 pH
was employed. Also, all glassware was washed and dried with
3.1.5 VISCOSITY
nitrogen.
4.5.0.5.
second method was via DSC analysis. The DSC method was under
the temperature range from -80oC and 40oC. Again, the data was
55
The boiling points of the DESs were determined using DSC. The
3.2.1 DENSITY
1.6
1.4
1.2
1.0
0.8
Aq ChCl Lit DES ILs
ChCl:H2O DESs.
1.4900
y = 0.9787x + 0.3709
1.4800 R² = 0.9783
Refractive Index
1.4700
1.4600
1.4500
1.4400
1.4300
1.4200
1.4100
1.4000
1.05 1.06 1.07 1.08 1.09 1.1 1.11 1.12 1.13 1.14
Density(g/cm3)
the RI of water.
3.2.3 VISCOSITY
values of DESs.
900
y = 1582.8x + 23.529
800 R² = 0.8478
Viscosity(mPa.s)
700
600
500
400
300
200
100
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Molar fraction of ChCl
900
800 y = 9363.9x - 9836.5
Viscosity (cP)
R² = 0.8814
700
600
500
400
300
200
100
0
1.05 1.06 1.07 1.08 1.09 1.1 1.11 1.12 1.13 1.14
Density (g/cm3)
3.
0.4
0.2 -38.22°C
-59.42°C
Heat Flow (W/g)
0.0
-48.23°C
17.87J/g
-0.2 2816 J/mole
-0.4
-0.6
-100 -80 -60 -40 -20 0 20 40
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.6
0.4
0.2
-33.59°C
Heat Flow (W/g)
-59.52°C
0.0 -65.00°C
-44.56°C
11.51J/g
-0.2 -67.92°C
-0.4
-84.67°C
3.160J/g
-0.6
-100 -80 -60 -40 -20 0 20
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.2
-78.29°C
-1.61°C
0.0 -91.24°C -2.10°C
26.10J/g 0.01607J/g
Heat Flow (W/g)
-0.2
-86.33°C
-0.4
-100 -80 -60 -40 -20 0 20 40
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.2
0.1
Heat Flow (W/g)
0.0
-78.43°C
-61.38°C
-0.1 23.78J/g 0.08699J/g
-58.78°C
-0.2
-90.62°C
-0.3
-100 -80 -60 -40 -20 0 20 40
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.4
0.2
Heat Flow (W/g)
-59.38°C
0.0 -74.63°C
0.05454J/g 7.35°C
-92.48°C
27.25J/g -74.03°C
4.31°C
0.08853J/g
-0.2
-89.44°C
-0.4
-100 -80 -60 -40 -20 0 20 40
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.4
-64.73°C
Heat Flow (W/g)
0.0
-76.58°C
1.47°C
0.2642J/g
-41.77°C
-0.2 -85.07°C
12.27J/g
3.33°C
-0.4
-0.6
-100 -80 -60 -40 -20 0 20
Exo Up Temperature (°C) Universal V4.5A TA Instruments
0.4
0.2 -59.00°C
-71.87°C
7.046J/g
Heat Flow (W/g)
0.0
-80.99°C
-39.01°C
-0.2
-57.88°C
-0.4
-81.08°C
11.92J/g
-0.6
-100 -80 -60 -40 -20 0 20 40
Exo Up Temperature (°C) Universal V4.5A TA Instruments
a rate of 10oC/min.
of these solvents.
-50
0 0.1 0.2 0.3 0.4 0.5 0.6
-55
Temperature (oC)
-60
-65
-70
-75
-80
-85
Mole fraction of ChCl
methods. Though the profiles look similar the DSC data are
slightly elevated.
66
studied solvents.
heat.
The most thermally stable solvents with the least weight loss
other solvents.
68
the higher the water content, the less thermally stable the
25
20
Heat Flow (W/g)
15
10
4.46°C
-3.51°C 1705J/g
346.7J/g
0
-50 0 50 100 150 200 250 300
Exo Down Temperature (°C) Universal V4.5A TA Instruments
1.5
Heat Flow (W/g)
1.0
66.66°C
0.5
65.69°C
119.5J/g
0.0
-50 0 50 100 150 200 250 300
Exo Down Temperature (°C) Universal V4.5A TA Instruments
234 19
ChCl:H2O(1:1)
235 95
221 12.5
ChCl:H2O(1:2)
224 74
234 26
ChCl:H2O(1:3)
236 91
107 25
ChCl:H2O(1:4)
294 33
104 29
ChCl:H2O(1:5)
247 99
107 32
ChCl:H2O(1:6)
240 98
102 41
ChCl:H2O(1:8)
232 96
107 49
ChCl:H2O(1:10)
245 99
71
H2O 0 145
12000
10000
(ChCl)
(1:1)
8000
TG(μg)
(1:2)
6000 (1:3)
(1:4)
4000
(1:5)
(1:6)
2000
(1:8)
0 (1:10)
0 50 100 150 200 250 300 350 400
Temperature(oC)
Figure 3.5. TGA thermogram of all ChCl:H2O DESs. All DESs lost
over 90% of their mass at 250oC except the 1:4 molar ratio.
73
3.3.1 INTRODUCTION
3.3.2 SOLVATOCHROMISM
(solvatochromism)113.
a red shift.
hexafluoro-2-propanol115-116.
polarity.
solute.
∆𝐻−𝑅𝑇
δH =√ Equation 3. 2
𝑉𝑚
δH = Hildebrand solubility
ET(30)= cν
–
O
O
+
+ N
N
zwitterions.
solvent124, 127 .
3.5 METHODOLOGY
The samples were scanned between 180 and 720 nm over the
CH3
O O N
CH3
N
+ +
– N N
–
O O O O
A B C
Figure 3.6.1. The three dyes used for the solvatochromic
N,N-diethyl-4-nitroaniline(C).
82
Reichardt119
ℎ𝑐𝑉𝑚𝑎𝑥 𝑁𝐴
h = Plank’s constant
c = Speed of light
Vmax = Wavenumber
NA = Avogadro’s constant
between 30.7 kcal/mol for TMS and 63.1 kcal/mol for water. To
avoid the use of the non-SI unit kcal/mol and use SI units,
𝐸𝑇 (𝑠𝑜𝑙𝑣𝑒𝑛𝑡)−𝐸𝑇 (𝑇𝑀𝑆)
𝐸𝑇𝑁 = Equation 3. 5
𝐸𝑇 (𝑤𝑎𝑡𝑒𝑟)−𝐸𝑇 (𝑇𝑀𝑆)
𝐸𝑇 (𝑠𝑜𝑙𝑣𝑒𝑛𝑡)−30.7
≈ Equation 3. 6
32.4
Unlike the ET(NR)scale, ETN scale ranges between 0.00 for TMS
dyes respectively.
85
ET(NR)values.
0.89
0.88
(1:1)
0.87
(1:2)
0.86 (1:3)
ETN
0.85 (1:4)
(1:5)
0.84
(1:6)
0.83
(1:8)
0.82
(1:10)
25 30 35 40 45
TEMPERATURE(oC)
0.86 (1:1)
0.84 (1:2)
0.82 (1:3)
α
0.8 (1:4)
0.78 (1:5)
0.76 (1:6)
25 30 35 40 45 (1:8)
TEMPERATURE(oC) (1:10)
0.46
0.44 (1:1)
0.42 (1:2)
0.4
(1:3)
0.38
β
0.36 (1:4)
0.34 (1:5)
0.32
(1:6)
0.3
25 30 35 40 45 (1:8)
TEMPERATURE(oC) (1:10)
0.77
(1:1)
0.76
0.75 (1:2)
0.74 (1:3)
π*
0.73 (1:4)
0.72 (1:5)
0.71
(1:6)
0.7
25 30 35 40 45 (1:8)
TEMPERATURE(oC) (1:10)
0.00
1.00 DES
IL
Org Sol
0.25
0.75
b
0.50
0.50
0.75
0.25
1.00
0.00
0.00 0.25 0.50 0.75 1.00
p*
Figure 3.6.5. Comparison of the Kamlet-Taft parameters of
(green).
3.7 CONCLUSION
that of water but the higher the water content, the closer
different.
DES(Figure 3.6.5).
91
CHAPTER FOUR
studies136-139.
DESs141.
and urea form the H-bonds that is known to be the major force
formation.
bonds. The small size of the HBD should amplify the hydrogen
bonds between the HBD and HBA due to the short distance
ratios of HBD and HBA needed to form the DES. This avoids the
ℏ2
[ ∑𝑁 2 𝑁 𝑁
𝑖−1 𝛻𝑖 + ∑𝑖−1 𝑉(𝑟𝑖 ) + ∑𝑖−1 ∑𝑗<𝑖 𝑈(𝑟𝑖 , 𝑟𝑗 )] ѱ = 𝐸ѱ Equation 4. 1
2𝑚
m= mass of electron
N= Number of electrons
r= Position vector
V= Potential energy
ℏ2
[ 2 𝛻 2 + 𝑉(𝑟) + 𝑉𝐻 (𝑟) + 𝑉𝑋𝐶 (𝑟)] ѱ𝑖 (𝑟) = 𝜀𝑖 ѱ𝑖 (𝑟) Equation 4. 3
VH is mathematically expressed as
𝑛(𝑟 ′ )
𝑉𝐻 (𝑟) = 𝑒 2 ∫ |𝑟𝑟 ′ | 𝑑 3 𝑟 ′ Equation 4. 4
𝛿𝐸𝑥𝐶 (𝑟)
𝑉𝑋𝐶 (𝑟) = Equation 4. 5
𝛿𝑛(𝑟)
polarity153.
4.2 COSMO-RS
4.2.1 METHODOLOGY
(Leverkusen, Germany).
conditions.
temperature.
𝑥
𝐸𝑣𝑑𝑤 ≅ ∑𝛼 𝜏𝑒𝑙(𝛼) 𝐴𝛼𝑥 or
′
𝐸𝑣𝑑𝑤 = 𝑎𝑒𝑓𝑓 (𝜏𝑣𝑑𝑤 + 𝜏𝑣𝑑𝑤 ) Equation 4. 6
where,
α= general constant
by;
102
Where,
(𝜎 + 𝜎 ′ ) = net charge
bond
HBA)
X in solvent S is calculated as
where,
𝑥
𝛾𝑐𝑜𝑚𝑏,𝑠 = combinatorial activity coefficient
𝑝𝑥 (𝜎 ) = σ-profile of 𝑋
𝑥
𝑥𝑖 𝑝𝑠 𝑖 (𝜎)
𝑝𝑠 (𝜎) = ∑𝑖 Equation 4. 10
𝑥𝑖 𝐴 𝑥𝑖
−𝑎𝑒𝑓𝑓 𝑒(𝜎,𝜎 ′ )
𝑙𝑛𝛾𝑠 (𝜎) = −𝑙𝑛 [∫ 𝑑𝜎 ′ 𝑝𝑠 (𝜎)𝛾𝑠 (𝜎 ′ ) × 𝑒𝑥𝑝 { }] Equation 4. 11
𝑅𝑇
𝑖
𝑙𝑛𝛾𝑖/𝑠 = 𝑛𝑖 ∑𝜎𝑚 𝑝𝑖 (𝜎𝑚 )[𝑙𝑛𝛾𝑠 (𝜎𝑚 ) − 𝑙𝑛𝛾𝑖 (𝜎𝑚 )] + 𝛾𝑐𝑜𝑚𝑏,𝑠 Equation 4. 12
104
𝑖
𝛾𝑐𝑜𝑚𝑏,𝑠 = combinatorial activity coefficient
A1 A2
4
1
2
5
3
B1 B2
(yellow)].
106
C1 C2
D1 D2
10
0
-0.03 -0.02 -0.01 0 0.01 0.02 0.03
-5
Screening charge density σ(e/Nm2)
ChCl:H2O (1:3) and ChCl:H2O (1:4) are almost the same but with
0.15
HBD 0.1 HBA
σ-potential(μ)[kcal/mol
0.05
0
-0.02 -0.015 -0.01 -0.005 -0.05 0 0.005 0.01 0.015 0.02
-0.1
A2]
-0.15
-0.2
-0.25
-0.3
-0.35
Screening charge density σ (e/Nm2)
CHCL CHCL_1H2O CHCL_2H2O CHCL_3H2O CHCL_4H2O
6
HBD REGION
HBA REGION
Sigma Profile p(σ)
0
-0.03 -0.02 -0.01 0 0.01 0.02 0.03
-1
Screening charge density σ(e/Nm2)
Figure 4.4. The hydrogen bonding profile within H2O, ChCl and
of hydrogen bonds.
111
this suggestion.
the ChCl:H2O (1:3) and ChCl:H2O (1:4) are almost the same. The
systems.
112
20
10
0
-0.03 -0.02 -0.01 0 0.01 0.02 0.03
-5
Screening charge density σ(e/Nm2)
CHCL CHCL_1H2O CHCL_2H2O CHCL_3H2O CHCL_4H2O H2O
5
4
2
𝑞𝐴 = 𝑍𝐴 − ∫ 𝜌𝐴 (𝑟)𝑑𝑟 Equation 4. 13
𝑞𝐴 = Charge of atom A
SOLVENTS
ATOM ChCl 1:1 1:2 1:3 1:4
Cl -0.644 -0.525 -0.514 -0.42 -0.437
N 0.096 0.097 0.097 0.098 0.097
O -0.219 -0.214 -0.219 -0.224 -0.218
C5 0.01 0.005 0.012 0.005 0.012
C4 -0.015 -0.008 -0.01 -0.008 -0.01
C3 -0.034 -0.034 -0.033 -0.032 -0.033
C2 -0.042 -0.04 -0.046 -0.046 -0.047
C1 -0.041 -0.038 -0.043 -0.036 -0.044
115
SOLVENTS
O -0.306 -0.307
H 0.086 0.091
H 0.152 0.155
O -0.258
H 0.173
H 0.066
in DESs.
ChCl:H2O (1:3) than the rest of the solvents (see Table 4.1).
proximally closer to the Cl- than the C2. Thus, these two
(1:3).
𝑄𝐴 = VDD charge
into atom/bond.
118
SOLVENTS
ATOM
ChCl 1:1 1:2 1:3 1:4
From Table 4.4, the main direction and flow of charge is from
et al. (2003) that charge flow from the halide ion induces
N 0 2 2 1
O 6 0 -3 1
C5 -1 -1 -5 0
C4 7 1 3 1
C3 -1 0 3 1
C2 1 -1 1 -2
C1 -1 -3 1 -2
4.4 CONCLUSION
develop Cosmo files for each solvent, and carrying out charge
backbone.
Cl- ions.
iii. This causes the Cl- ions to form weak interactions with
iv. These interactions between the Cl- ions and the H atoms
bonding.
121
CHAPTER FIVE
other solvents.
transfer analyses.
charge emanates from the halide ion, and the strength of the
this.
126
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