SUPPLEMENTARY DATA FOR:
Valorization of monosaccharides towards fructopyrazines in a new sustainable and efficient eutectic medium
Svitlana Filonenko*, Antje Foelkel and Markus Antonietti
Max Planck Institute of Colloids and Interfaces Research Campus Golm14424 PotsdamGermany
Corresponding Author E-mail: [email protected]
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2019
Materials
Saccharides arabinose (Alfa Aesar, 99%), xylose (Roth, 99%), glucose (Roth, 99%), fructose (Sigma-Aldrich, 99%), mannose (Alfa Aesar, 99%), galactose (Roth, 97%), sucrose (Sigma-Aldrich, 99%), maltose (Roth, 99%) were used without further purification. Due to the high hydrophobicity, ammonium formate (Alfa Aesar, 98%) was dried in the vacuum oven at room temperature for 24 hours prior the use in reaction.
Table S1. Composition of the eutectic mixtures
Entry Sample Type of saccharide Saccharides used as HBD component
Ratio saccharide /ammonium formate
1 EM-A arabinose 1:1
2 EM-Xpentoses
xylose 1:1
3 EM-G glucose 1:0.5, 1:0.75, 1:1, 1:1.2, 1:1.5
4 EM-F fructose 1:1
5 EM-Man mannose 1:1
6 EM-Gal
hexoses
galactose 1:1
7 EM-S sucrose 1:2
8 EM-Maldisaccharides
maltose 1:2
2.53.03.54.04.55.05.56.06.57.07.58.08.5δ/ ppm
6.43
1.01
1.00
8.14
8.27
8.40
8.55
2.53.03.54.04.55.05.56.06.57.07.58.08.5δ/ ppm
4.26
1.03
1.00
8.13
8.20
8.45
8.63
0102030405060708090100110120130140150160170180190200210δ/ ppm
0102030405060708090100110120130140150160170180190200210δ/ ppm
Fig. S1. 1H and 13C NMR spectra (D2O) of reaction mixture of ammonium formate with glucose, representing formation of 2,6-DOF (A and C, respectively), and ammonium formate with fructose, representing 2,5-DOF formation (B and D, respectively). The signals in 1H are not allowing distinguishing between the formation of 2,5-DOF and 2,6-DOF, while 13C NMR spectra give a different signals.
C
D
A
B
Pyrazine ring carbons
Pyrazine ring carbons
2.53.03.54.04.55.05.56.06.57.07.58.08.5δ/ ppm
2.50
DM
SO
8.25
0102030405060708090100110120130140150160170180190200210δ/ ppm
N
N OOO
O
O
O
O
H H
HH
HH
H H
HH
HH HH
H
H
H
H
H
Fig. S2. 1H and 13C NMR spectra (d6-DMSO) of crude reaction mixture of ammonium formate with glucose after freeze drying, representing formation of 2,6-DOF (A and B, respectively); the signal at 8.25 ppm corresponds to protons of formate anions ionically bonded to 2,6-DOF; 1H spectrum (D) predicted for the structure of 2,6-DOF (C). 1-3
C
D
A
B
0 day 1 day 2 day 3 day 4 day 5 day 7 day 14 day
Fig. S3. Physical occurrence of the ammonium formate / glucose mixture kept at room temperature over time
2.53.03.54.04.55.05.56.06.57.07.58.08.5δ/ ppm
0102030405060708090100110120130140150160170180190200δ/ ppm
2.53.03.54.04.55.05.56.06.57.07.58.08.5δ/ ppm
0102030405060708090100110120130140150160170180190200δ/ ppm
Fig. S4. 1H and 13C NMR spectra of the mixture of ammonium formate with glucose kept at room temperature for five days (A and B, respectively) and two weeks (C and D, respectively) representing different degree of 2,6-DOF formation.
C
D
A
B
2.53.03.54.04.55.05.56.06.57.07.58.08.59.0δ/ ppm
8.08.18.28.38.48.58.68.78.88.99.0δ/ ppm
Fig. S5. In situ 1H NMR spectra as a function of reaction time for the fructose transformation in eutectic medium in isochoric process at 80 °C.
0 min
60 min
30 min
90 min
120 min
150 min
180 min
210 min
270 min
Fig. S6. Identification of reaction products by UHPLC-MS method: representative UHPLC chromatogram of reaction mixture of ammonium formate with mannose (A), galactose (B), arabinose (C), xylose (D) incubated at 90 °C for 4 hours, and product ion scans (MS/MS spectra) corresponding to respective pyrazine derivatives formed.
C
D
A
B
Fig. S7. Identification of reaction products by UHPLC-MS method: representative UHPLC chromatogram of reaction mixture of ammonium formate with sucrose (A), maltose (B), incubated at 90 °C for 4 hours, and product ion scans (MS/MS spectra) corresponding to respective pyrazine derivatives formed
A
B
Hexoses
Pentoses
Disaccharides
Fig. S8. Formulas of corresponding saccharides and the 1H NMR spectrum of bare mixture after reaction with ammonium formate for 4h at 90 °C: glucose (A), fructose (B), mannose (C), galactose (D), arabinose (E), xylose (F), sucrose (J), maltose (K).
mannose galactosefructose
arabinose
maltosesucrose
xylose
A
A
A
B
C
D
E
F
J
K
Fig. S9. TGA–MS weight loss and derivative of weight loss curves for ammonium formate / glucose mixture (A); mass spectra from thermal dermal decomposition of ammonium formate / glucose mixture (B)
100 200 300 4000
10
20
30
40
50
60
70
80Mass fragments m/z = 16 m/z = 17 m/z = 18 m/z = 29 m/z = 44
Temperature, °C
Ion
curr
ent,
10-1
0 A
20
40
60
80
100
Mas
s lo
ss, %
100 200 300 400
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0,40
0,45Mass fragments m/z = 12 m/z = 30 m/z = 15 m/z = 45 m/z = 19 m/z = 46 m/z = 20
Temperature, °C
Ion
curr
ent,
10-1
0 A
20
40
60
80
100
Mas
s lo
ss, %
50 100 150 200 250 300 350 40020
40
60
80
100
TGA
Temperature, °C
TGA %
DTG mg/min
-0,30
-0,25
-0,20
-0,15
-0,10
-0,05
0,00
DTG
A
B
Fig. S10. DSC measurement of fructose / ammonium formate mixture in temperature range from -90 to 60 °C, heating/cooling rate is 10.0 °C/min; sample was heated from room temperature to 60 °C in order to form the eutectic mixture and cooled down immediately to avoid the reaction between the components
200 300 400 500 600
0,0
0,5
1,0
reaction temperature 60 C reaction temperature 80 C reaction temperature 90 C reaction temperature 100 C
N
N
R1,R2Ab
sorb
ance
/ a.
u.
Wavelength / nm
275
Fig. S11. UV-vis spectra of eutectic mixture solutions after reaction showing formation of (polyhydroxyalkyl)pyrazines formation.
4000 3500 3000 2500 2000 1500 100070
80
90
100
90
Tran
smitt
ance
/ %
50
100Tr
ansm
ittan
ce /
%
c
b
Tran
smitt
ance
/ %
/ cm-1
aC N N
N
R
Fig. S12. FTIR spectra of eutectic mixture of glucose with ammonium formate after reaction (a), pristine glucose (b) and ammonium formate (c).
References
1. Banfi, D.; Patiny, L. www.nmrdb.org: Resurrecting and processing NMR spectra on-line Chimia, 2008, 62(4), 280-281. 2. Andrés M. Castillo, Luc Patiny and Julien Wist. Fast and Accurate Algorithm for the Simulation of NMR spectra of Large Spin Systems. Journal of Magnetic Resonance 2011. 3. Aires-de-Sousa, M. Hemmer, J. Gasteiger, “ Prediction of 1H NMR Chemical Shifts Using Neural Networks”, Analytical Chemistry, 2002, 74(1), 80-90.