In vitro Conversion of Vinyl to Formyl Groups in Naturally Occurring
Chlorophylls
Patrick C. Loughlin1, Robert D. Willows2 and Min Chen1
1
School of Biological Sciences, University of Sydney, NSW 2006, Australia
Department of Chemistry and Biomolecular Sciences, Macquarie University, NSW 2109,
Australia
2
1
Supplementary information
Table S1. 1H (600 MHz) and 13C (150 MHz) NMR data of the C31-sulfoxide of β-mercaptoethanol
derivative of Chl a in CDCl3 with 0.5% d5-pyridine. Reference to CHCl3 (d in ppm, J in Hz). Data
assigned by combination of 1H-1H, HMBC and HSQC spectra.
dC
Entry (Carbon)
1
154.3
132
2
136.2
133
11.3
134
141.5
14 or 16
162.2
Entry (Carbon)
21
dH
3.22 (3H, s)
3
dH
6.21 (1H, s)
dC
65.6
170.8
3.85 (3H, s)
52.8
31
6.13 (1H, broad m)*
69.4
15
105.0
32
2.89 (3H, broad)*
36.0
16 or 14
162.2
1-BME
3.42 (1H, m)
41.7
17
50.5
2.47 (m), 2.28 (m)
30.0, 29.8
2.33 (m), 1.90 (m)
30.2, 30.7
1’-BME
3.61 (1H, m)
41.9
2-BME
3.87 (m)
61.0
172 and 172’
2’BME
3.81 (m)
61.4
173
5
9.48 (1H, d)*
101.1
18
4.35 (1H, q, 7.3)
49.3
6
152.0
181
1.63 (3H, t*, 7.3)*
23.2*
7
134.3
19
11.3
20
8.3 (1H, d)*
92.4
P1
4.44 (1H, q, 5.9)
61.4
P2
5.125 (1H, t, 5.9)
117.7
71
3.26 (3H, d)*
8
3.74 (2H, q, 7.7)
82
1.68 (3H, t, 7.7)
9
17.3
144.6
9.57 (1H, s)
107.0
11
147.9
12
135.2
121
173.2
168.4
144.4
81
10
and
4.115 (1H, d, 7.6)
171’
171
3.65 (3H, s)
143.0
P3
1.90 (HSQC)
39.7
1.1 (m)
39.2
P15
1.48 (H, n, 13.3, 6.6)
28.0
P16 and P17
0.83 (6H, d, 6.6)
22.8
0.78 or 0.80 (total of
6H, d, 6.6)*
1.58 (3H, s)
19.7
P4
P14
13
130.8
P18 and P19
131
190.2
P20
16.5
Notes: 171 and 172 have different conformers as described previously for chlorophyll a and chlorophyll f (see Smith
et al 1984, and Willows et al 2012).
*P18 and P19 0.79 and 0.81 appear as single correlations at 0.80 in HSQC.
one or more of P6, P8, P10, P12.
HSQC at 0.99 – 37.2; 1.19 – 37.2 are
Proton NMR has a water peak at 1.85.
Broadening and splitting of the 31 and 32 resonances due to different of diasteromers.
2
Figure S1. NMR spectra of the C31-sulfoxide β-mercaptoethanol of chlorophyll a. H1-H1, HSQC
and HMBC spectra are as labelled. * indicates water, chloroform and pyridine. HMBC long range
correlations are shown
H1-H1 spectrum of C31-sulfoxide β-mercaptoethanol of chlorophyll a
3
HSQC spectrum of C31-sulfoxide β-mercaptoethanol of chlorophyll a
4
HMBC spectrum of C31-sulfoxide β-mercaptoethanol of chlorophyll a. Structure shows long range
correlations
la
5
Figure S2. Matrix-assisted laser desorption/ionization-time-of flight spectra for the three formyl
products derived from 8-vinyl Chl a. Each chlorophyll has two major ions (marked in grey
boxes), the complete chlorophyll molecule (892.2 or 894.3 Da) and a more intense
fragmentation ion (-phytol) corresponding to the loss of the phytol tail (614.3 or 616.2 Da)
which is commonly observed for chlorophylls
6