Supporting Information
for
Fermentation of Aromatic Lactate Monomer and its Polymerization to Produce High
Thermoresistant Bioplastics
Hieu Duc Nguyen1,Tomoya Fujita2, Takashi Ito2, Naoki Takaya2, Tatsuo Kaneko1*
1. Schoolof Materials Science, Japan Advanced Institute of Science and Technology
1-1 Asahidai, Nomi, Ishikawa, 923-1292 Japan
Tel: +81-761-51-1631, Fax: +81-761-51-1635, e-mail: [email protected]
2. Faculty of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8572,
Japan
SUPPORTING INFORMATION
eH
Hf
e
COOH d
Hb
DMSO
g HO
OH a
eH
Hc
Hf
b
Hc
c
f
d
a
g
1
Figure S1. H-NMR spectrum of DHPA (400 Mhz, DMSO-d6): (because of shielding
effect, the hydroxyl peak (Ha) and carbonyl peak (Hd) is very broaden), peak of two
c with proton in
protons of methylene is composed of two doublet due to coupling
stereo center (Hb). The proton at stereo center (Hb) is a doubled triplet due to chiral
effect. Two triplet of methanediyl (Hc) δ ppm 2.76 (dtd, J=8.53, 5.27, 5.27, 2.51 Hz, 1
H), doubled triplet methine (Hb) δ ppm 4.15 (dt, J=7.91, 5.58 Hz, 1H, doublet of 2hydroxyδppm 5.50 (d, J=6.27 Hz, 1 H) , phenyl have two triplet Hf δppm 6.98 (d,
J=8.53 Hz, 2.26 Hz, 1 H) and He δppm 6.65 (d, J=8.53, 2.26Hz, 1H), p-hydroxy of
phenyl (Hg) singlet δppm 9.20 (s, 1H).
eH
Hf
COOMe
Me
g HO
OH a
Hc
eH
Hf
Hb
Hc
g
e
Water
f
a
f
b
c
Figure S2.1H-NMR spectrum of methylated DHPA: the methylation result is
confirmed by taking signal integration of methyl
a group to compare with signal
DMSO
f
integration of hydroxyphenyl, and the ratio of 3:4 is consistent
to
the number of
b
protons confirmed that no side reaction occurred at methyl ester group. The DHPAderived diol has singlet of methyl (-CH3) δppm 3.68.
DMSO
jH
MeOOC
eH
O
Hj
Hf
cH
eH
Hf
Hb
O
jH
Hc
Water
O
O
Hj
n
j
Me
ef
f
j
DMSO
b
c
Figure S3.1H-NMR spectra of monomer and PDHPA-co-TP Hb shifted from 4.3 ppm
to 5.5 ppm after esterification (also described in references 6, 7 and 16 in main
article). Doublet Hi δppm 8.15(d, J=8.78, 1 H) and Hj δppm 8.35(d, J=8.75, 1 H)
belong to terephthaloyl.
MeOOC
eH
O
iH
O
Hf
O
Water
O
Hf
Hj
Hb
Hc
eH
Hc
DMSO
Hj
Hk
Me
k jj
k k
i
ef
b
cc
Figure S4.1H-NMR spectra of monomer and PDHPA-co-IP. A singlet Hi δppm 7.75
(s, 1 H), a triplet Hk δppm 8.67 (t, J=14.86, 1 H), and a doublet Hj δppm 8.38 (d,
J=10.58, 2 H) belong to isophthaloyl.
Water
H
MeOOC
eH
H
O
Hf
O
H
H
Me
n
O
O
Hb
Hc
eH
H
H
H
Hc
Hf
H
DMSO
c
e f
b
Figure S5.1H-NMR spectrum of monomer and poly(methyl-4-hydroxyphenyllactateco-succinate) - PDHPA-4C
O
DMSO
H
MeOOC
eH
H
O
Hf
O
n
Me
H
H
O
H
H
H
Ha
Hb
eH
Hb
Hf
H
H
H
H
H
f e
c
b
Water
Figure S6.1H-NMR spectrum of monomer and poly(methyl-4-hydroxyphenyllactateco-glutarate) - PDHPA-5C
H
eH
H
H
MeOOC
O
H
O
Hf
H
n
H
DMSO
O
H
H
H
H
O
Hc
eH
Hf
Hb
H
H
Me Water
Hc
H
H
H
H
e f
b
c
Figure S7.1H-NMR spectrum of monomer and poly(methyl-4-hydroxyphenyllactateco-adipoate) - PDHPA-6C
O
H
MeOOC
eH
Me
H
H
H
O
Hf
O
H H
n
H
H H
H H
H
H
H
O
Hc
eH
Hf
H
Hb
H
H H
Hc
e
f
H H
acetone
c
b
Figure S8.1H-NMR spectrum of poly(methyl-4-hydroxyphenyllactate-co-pimeloate) PDHPA-7C
hH
hH
O
Hh
DMSO
Hh
MeOOC
eH
Hh
O
Hf
hH
O
n
Hh
H H
hH
H H
H
H
Hh
hH
O
Ha
Hb
eH
Hf
hH
Hh
Hb
e e
b
Me
Water
c
H H
H H
H H
Figure S9.1H-NMR spectrum of poly(methyl-4-hydroxyphenyllactate-co-suberate) PDHPA-8C
O
kH
Hk
MeOOC
eH
Hk
O
Hf
O
kH
Hh
n
Hh
Hf
hH
Hb
Hc
eH
Actone
Me
Hh
Hh
O
H H
Hh
H H
H H
H H
Hc
e
H H
e
b
H H
H H
c
Figure S10. 1H – NMR spectrum of poly(methyl-D hydroxyphenyllactate-coazeloate) - PDHPA-9C
3500
-C-H stretch of
alkyl
-C-H stretch of
3000
2500
aromatic ring
2000
C=O stretch
of ester
3500
3000
2500
2000
1500
1000
500
1000
500
C-C stretch
of aromatic
C=C bend
of aromatic
1500
Figure S11.FT-IR spectra of aromatic-coperated DHPA polyesters. FT-IR spectra of
aromatic-coperated DHPA polyesters. Aromatic ring of DHPA and phenylene of
phthalates were indicated by the C-H stretch of the appeared at 3099 (cm-1), together
with C=C bending at 1650 (cm-1) and C-C stretch at 1465 to 1506 (cm-1). C=O
stretch indicated ester bonds appear at 1726 (cm-1). -C-H stretch of alkyl appeared at
2925 (cm-1)
0
0
0
0
0
0
0
4C
5C
3500
3000
2500
2000
1500
1000
500
6C
3500
3000
2500
2000
1500
1000
500
7C
3500
3000
2500
2000
1500
1000
500
8C
3500
3000
2500
2000
1500
1000
500
9C
3500
3500
-C-H stretch of
-C-H3000
stretch ofalkyl 2500
aromatic
ring
3000
2500
10C
2000
1500
1000
500
2000
1500
1000
500
C=O stretch
of ester
3500
3500
3000
3000
2500
2500
C=C bend
2000
2000
1500
1500
-C-H stretch of aromatic ring
1000
1000
500
500
FigureS12.FT-IR spectra of aliphatic-coperated DHPA polyesters. FT-IR spectra of
aromatic-coperated DHPA polyesters. Aromatic ring of DHPA of phthalates was
indicated by the C-H stretch of the appeared at 3099 (cm-1), together with C=C
bending at 1650 (cm-1) and C-C stretch at 1465 to 1506 (cm-1). C=O stretch indicated
ester bonds appear at 1726 (cm-1). -C-H stretch of alkyl appeared at 2925 (cm-1).
TP
IP
Figure S13.GPC curve of DHPA-co-TP (the slide in red rectangular is the calculated
peak). The main polymer fraction peak appeared at 38 minute on retention time scale
(around 10,000 g/mol). The higher molecular-weight overlaps peaks appeared from 22
to 30 minute on retention time scale indicates the result of minor transesterifications
during polymerization.