Supplementary material to this book contains the following Adobe-Writer (.pdf) files: an overview of the material, the color coding for the map on the title page), and supporting information for chapter 1, 14, 20, 22 and 30. Some of the files contain further links to materials on this server, in particular is there a collection of structural formulas accessible from the material to chapter 1.

Please, click on the respective files for downloading. Any reference should cite the full title of the book

Grimm, Bernhard

Porra, Robert J.

Rüdiger, Wolfhart

Scheer, Hugo

English

Open Access LMU

 Bernhard Grimm, Humboldt University, Berlin, Germany; Robert J. Porra, CSIRO Plant Industry, Canberra, ACT, Australia; Wolfhart Rüdiger, München University, München, Germany; Hugo Scheer, München University, München, Germany (Eds.)   Chlorophylls and Bacteriochlorophylls Biochemistry, Biophysics, Functions and Applications Chlorophylls are the most obvious natural pigments on Earth where they can be observed even from satellites in  outer space: they also sustain life on Earth through their involvement in photosynthesis. With 37 authoritative  chapters, this book reviews recent progress and current status of studies on the chemistry, metabolism and  spectroscopy of chlorophylls, bacteriochlorophylls and their protein complexes. Also discussed is progress on the  applications of the chlorophylls as photosensitizers in photodynamic therapy of cancerous tumours, and as  molecular probes in biochemistry, medicine, plant physiology, ecology and geochemistry. With the last book  dedicated to chlorophylls published in 1991, and out of print since 1995, this book fills a gap by summarizing the  chemical, physical, biological and medical aspects of chlorophyll (and bacteriochlorophyll) research and  development, with a focus on the tremendous progress achieved over the past 15 years. The book is aimed equally  at advanced students and at both novice and experienced researchers: each section has an up-to-date introductory  overview which is followed by a series of concise, well-focused and fully-referenced chapters written by experts in  (bio)chemistry, (bio)physics, photobiology and photomedicine.      From the reviews: “This excellent book provides a comprehensive, up to date account of the chemistry  and biology of chlorophylls and bacteriochlorophylls, written by world experts.  Progress in the past few years in this area of science, especially on how these pigments are synthesised and degraded, and how they function in photosynthesis, has been remarkable. All of these recent advances are beautifully set out in this timely compendium, which is, at the same time, both  very readable and very complete. The Editors are to be congratulated. It is interesting to see how fundamental research in this area has led to important, unexpected applications such as the treatment of cancers by photodynamic therapy or remote sensing of photosynthetic capacity from outer space. This will be essential reading for all of my research team and, I expect, for every other research group that works with these fascinating molecules.” Prof. R.J. Cogdell, University of Glasgow, Scotland, UK  ”The attempt to understand the perfection of the chlorophylls is the central theme of this book.  In today’s energy hungry world with renewed interest in solar energy, this collection on the chlorophylls is most timely, covering the latest aspects of chlorophyll research through the scholarship of 70 authorities. With the role of chlorophyll and bacteriochlorophyll in photosynthesis as revealed in these pages, the reality of practical applications of solar energy trapping and conversion becomes an intriguing possibility. These applications will go far beyond the biological process of photosynthesis to include such topics as solar energy conversion, environmental science, medical applications, cosmetics, sun screens, etc. Many of these applications are included in this comprehensive volume. Many new applications will arise as a result of this outstanding collection on the functions and applications of chlorophylls and bacteriochlorophylls.” Prof. James R. Norris, University of Chicago, Illinois, USA  2006 Approx. 640 p. Hardcover , Forthcoming Advances in Photosynthesis and Respiration (Series Editor, Govindjee), Volume 25  ISBN 1-4020-4515-8 • $ 253.00 Special discount price ISPR $ 189.75 forthcoming       ISBN 1-4020-4515-8 • $ 253.00  Grimm,B. et al (Eds): Chlorophylls and Bacteriochlorophylls (Adv. Photosyn. Respir. 25)    ISBN 1-4020-4515-8        • $ 189.75 Special 25% discount price ISPR   

Chlorophylls and Bacteriochlorophylls: Biochemistry, Biophysics, Functions and Applications

Universität München: Elektronischen Publikationen

E:\Text\Publ\NewChls\DeBoer-Degroot\Chapter 20 DeBoer DeGroot Supplement.doc 0 von 15 8/20/2006 
Chlorophylls and Bacteriochlorophylls: Biochemistry, Biophysics, Functions and 
Applications 
B. Grimm, R. Porra, W. Rüdiger, H. Scheer (eds.) 
 
Vol. 25 of Advances in Photosynthesis and Respiration 
Govindjee (series editor) 
 
Published 2006 by Springer, ISBN 1-4020-4515-8 
 
 
Supplement to chapter 20 
MAS NMR of the Chlorosomes (I. de Boer, H. J.M. de Groot) 
 
 
MAS NMR of the chlorosomes (web appendix) 
 
Ido de Boer‡, Huub J. M. de Groot‡* 
 
‡Leiden Institute of Chemistry, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, 
The Netherlands 
*Corresponding author. Fax: +31715274603 E-mail: groot_h@chem.leidenuniv.nl 
 
 
 
 
Table of contents 
  
I .   Magic Angle Spinning NMR methods for structure determination 
 
A.    Fast Magic Angle Spinning NMR in high magnetic field 
B.    Homonuclear correlation spectroscopy 
C. Heteronuclear correlation spectroscopy 
 
II.    Chemical shift data of 13C enriched Chl a/H2O and chlorosomal BChl c 
 1
I.    Magic Angle Spinning NMR methods for structure determination 
A.    Fast Magic Angle Spinning NMR in high magnetic field 
  Magic Angle Spinning (MAS) NMR structure determination of multispin labeled solids 
critically depends on both the resolution and stability that can be achieved with the NMR 
spectrometer. In both aspects, important improvements have been realized in the past few 
years. The resolution was improved by fast MAS, high field and modern pulse 
technology. In particular, the recent realization of ultra high field spectrometer 
technology has boosted the development and implementation of novel structure 
determination methodology. The stability required to perform the new generation of 
experiments was achieved by improvements in the spectrometer electronics hardware, 
allowing fast, precise and coherent phase and frequency switching during the NMR 
experiment. 
 
  To describe the NMR, the Hamiltonian 
 ISIICSS HHHH ++=  (1) 
is used (Mehring, 1983). HCS is the chemical shift term, HII contains the homonuclear 
dipolar couplings and HIS represents the heteronuclear dipolar couplings. Anisotropic spin 
interactions that are averaged to an isotropic part in liquids cause large NMR line 
broadening in solids. These are primarily the anisotropic part of the chemical shift and 
the dipolar spin-spin couplings. The chemical shift σ, for example, depends on the 
orientation of the chemical environment of the nucleus in the magnetic field. 
  
  The anisotropic interactions in solids can be eliminated by fast rotation of the sample 
around an axis at the magic angle θm ≈ 54.74° with the static field . For instance, for the 
chemical shift it can be shown that the time dependent transformation from the principal 
axis frame to the laboratory frame leads to a time average of  
 ( ) ( ) z0isoz0221isozz 1cos32 IBIBH CS σθσσ +−+= , (2) 
 2
where σzz is a tensor element, σiso is the isotropic component of σ, B0 is the magnetic 
field strength, θ is the angle between the rotor axis and B0 and Iz is a spin operator. The 
first term equals zero for θ =θm and only the isotropic term survives. 
  
  For MAS to be efficient, the spinning rate ωr needs to be much larger than the strength 
of the anisotropic interactions. The chemical shift scales with B0 (see Eq.[2]), while the 
dipolar couplings are field-independent. Thus, higher magnetic fields are generally 
desirable as the dispersion of the signals increases relative to the broadening effects of the 
dipolar couplings and the resolution is enhanced. In addition, high fields increase the 
sensitivity of the NMR experiments. Since the chemical shift anisotropy also scales with 
B0, fast MAS is necessary in high fields. With developments in instrumentation, MAS 
rates of ~15 kHz are now common practice and higher rates up to ~50 kHz are possible, 
although at the expense of smaller sample volumes. This is sufficient to reduce the 
chemical shift anisotropy as well as the homonuclear dipolar couplings between isotope 
labels such as 13C. 
  
  Many of the standard cross polarization (CP) experiments can be applied or have been 
adopted for use with rapid MAS in high field. The CP technique exploits the high 
abundance, high sensitivity and short relaxation times of the protons by transferring 
transverse 1H magnetization to another spin species (Hartmann and Hahn, 1962). The 
maximum enhancement for a 13C signal compared to direct 13C excitation is g1H/g13C ≈ 4. 
In addition, the recycle delay required for the accumulation of the free induction decays 
is usually short. Overall, CP introduces a significant gain in sensitivity. During the 
detection of the signal, heteronuclear decoupling is applied to achieve a high resolution. 
The robust TPPM sequence is now widely used for this purpose (Bennett et al., 1995). It 
uses 180° pulses with alternating phases for efficient decoupling. The CP/MAS 
experiment with TPPM decoupling is the building block for more advanced techniques, 
such as two-dimensional correlation spectroscopy. 
   
 3
B.    Homonuclear correlation spectroscopy 
  To resolve signals and for de novo structure determination of solids, correlation NMR 
spectroscopy of multi-spin labeled molecules is necessary. Here the homonuclear dipolar 
couplings, that are averaged by MAS to achieve a high resolution, are reintroduced 
during a mixing interval to generate correlated spin states (Mehring, 1983; Ernst et al., 
1987).  Two experiments that are widely used and important for the study of organic 
compounds are 13C-13C and 1H-13C correlation spectroscopy. The sequence of the 13C-13C 
Radio Frequency-Driven Dipolar Recoupling (RFDR) MAS correlation experiment 
(Bennett et al., 1992) is shown in Fig. S1A. The preparation step consists of the CP 
procedure. During t1 and t2, the 13C spins precess under heteronuclear decoupling to give 
a high resolution. During τm, however, the dipolar 13C-13C couplings have to be 
reintroduced to promote transfer of magnetization. The magnetization is first stored along 
z by a 90° pulse. The actual recoupling is achieved by a series of 180° pulses, which are 
synchronized with the rotor frequency. The evolution of the spin state ρ is determined by 
the commutator  
 [ ])(,~)( II tHidt
td ρρ −= , (3) 
where II
~H  is a spin Hamiltonian describing the effective reintroduced homonuclear 
dipolar interactions. This yields  
 )sin()()2/(sin)2/(cos)( m212121m
2
2m
2
1 dIIIIdIdIt yxxyzz τττρ −++= , (4) 
where d depends on the dipolar coupling strength (Bennett et al., 1992). The first two 
terms indicate transfer of longitudinal magnetization, while the third term represents 
double quantum states, which can be eliminated by phase cycling. If a short mixing time 
τm of ~1 ms is used, only correlations between spins separated by one bond in an organic 
molecule are created, which is most beneficial for the assignment of the chemical shifts. 
  
  To resolve intermolecular arrangements, incoherent processes over longer distances can 
be used to obtain distance constraints. For instance, the RFDR sequence with a long 
mixing time has provided 13C-13C correlations spanning larger distances (Boender et al., 
1995). Intermolecular transfer between 13C spins, however, is generally difficult for 
 4
uniformly labeled chlorophylls, due to rapid relayed spin diffusion along the multispin 
13C-labeled molecular network. An attractive alternative is to generate 13C-13C 
correlations by 1H spin diffusion (Mulder et al., 1998; Wilhelm et al., 1998). In this CP3 
experiment the 13C magnetization is transferred back to 1H after the first precession 
interval. Next, 1H spin diffusion is allowed to take place during a mixing period. Finally, 
the signal is transferred again to 13C by a third CP step and detected. In this way, mixing 
by the strong 1H dipolar interactions is combined with the high resolution of 13C. The 
diffusion experiment was used to determine a maximum effective transfer range dmax for 
short mixing times (de Boer et al., 2002). In this way intermolecular distance constraints 
were resolved. In practice, a limited number of constraints can already be very useful for 
elucidating the structure of ordered solids. 
 
C.    Heteronuclear correlation spectroscopy 
   
   A straightforward 1H-13C correlation experiment consists of the CP scheme, where t1 is 
inserted after the first 1H 90° pulse and the CP interval constitutes the mixing step. This is 
known as Wideline Separation (WISE), since broad 1H lines in the indirect dimension are 
separated by correlation with 13C shifts in the direct dimension. The homonuclear dipolar 
couplings between the abundant 1H spins are too strong to be eliminated, even in case of 
fast MAS. 
  
  Although 1H signals can be assigned with the WISE technique, the 1H resolution can be 
improved considerably if there is little inhomogeneous line broadening. In particular, the 
robust Lee Goldburg (LG) technique employs off-resonance rf irradiation to generate an 
effective rf field inclined at the magic angle (Lee and Goldburg, 1965; Bielecki et al., 
1989). Precession of the spins around this field amounts to “magic angle spinning in spin 
space”. With the 2D LG/MAS experiment (Fig.S1B), spectra can be obtained with a good 
resolution in both dimensions (van Rossum et al., 1997). A recent version uses phase 
modulated Lee Goldburg (PMLG), which is easy to implement compared to the 
frequency switched LG (Vinogradov et al., 1999). 
  
 5
  Heteronuclear distances were measured with the cross polarization and Lee Goldburg 
decoupling applied during the CP step to suppress 1H spin diffusion (van Rossum et al., 
2000). As a result, the Hamiltonian for a coupled 1H-13C spin pair during LG-CP 
simplifies to 
 ( ) ( )[ ]ϕϕδ iSIiSIH −+= +−−+ expexp4
~
IS , (5) 
where I± and S± are spin operators for the 1H and 13C spin, respectively. The dipolar 
coupling δ is given by 
 3
IS
2
SI0
m1 4
sin
r
G
hγγ
π
μ
θδ −=  , (6) 
with G1 a geometrical factor and rIS the distance between the spins. The coherent build-up 
of the 13C signal S(t) is then described by 
 ( )tTZktS δω 210I1B41 cos1)()( −−= − . (7) 
From the build-up of S(t) the dipolar coupling can be determined. This technique yields 
accurate distances up to a few Å. As the dipolar couplings scale with r-3, the effects of 
long-distance interactions are obscured by strong short-range interactions. For longer CP 
times, the magnetization transfer is incoherent due to the many spin interactions and 
relaxation. Although accurate intermolecular distances are difficult to determine in 
chlorophylls, incoherent long-range transfer proceeds over an effective maximum transfer 
range dmax, which depends on the length of the mixing period (van Rossum et al., 2002). 
  
  Finally, dilution of the 1H spins by 2H has been explored to reduce the 1H line widths of 
chlorophylls (Schulten et al., 1998). Obviously, the reduction in sensitivity is a major 
disadvantage of this method. With a dilution level of 75%, the 1H line widths in a 2D 
WISE experiment are narrowed significantly for several signals, although for the 
aliphatic protons there is little improvement. A 2D FSLG or PMLG experiment 
outperforms the 75% 2H dilution, since a better resolution is obtained without sacrifying 
sensitivity. 
 
 
 6
II.    Chemical shift data of 13C enriched Chl a/H2O and chlorosomal BChl c 
 
In Table S1 and S2, 1H and 13C chemical shift data is listed that were acquired by MAS 
NMR of solid aggregated [U-13C]-Chl a/H2O (Table S1) and [U-13C]-BChl c in the 
chlorosomes of Chlorobium tepidum (Table S2). A detailed account of these studies is 
given in the book chapter corresponding to this appendix. See also the references in the 
figure captions. 
 7
References 
 
Bennett AE, Ok JH, Griffin RG and Vega S (1992) Chemical-shift correlation   
  spectroscopy in rotating solids - radio frequency-driven dipolar recoupling and  
  longitudinal exchange. J Chem Phys 96: 8624-8627 
Bennett AE, Rienstra CM, Auger M, Lakshmi KV and Griffin RG (1995) Heteronuclear  
  decoupling in rotating solids. J Chem Phys 103: 6951-6958 
Bielecki A, Kolbert AC and Levitt MH (1989) Frequency-switched pulse sequences -  
  homonuclear decoupling and dilute spin NMR in solids. Chem Phys Lett 155: 341-346 
Boender GJ, Raap J, Prytulla S, Oschkinat H and de Groot HJM (1995) MAS NMR  
  structure refinement of uniformly C-13 enriched chlorophyll-a water aggregates with 2D   
  dipolar correlation spectroscopy. Chem Phys Lett 237: 502-508 
de Boer I, Bosman L, Raap J, Oschkinat H and de Groot HJM (2002) 2D C-13-C-13  
  MAS NMR correlation spectroscopy with mixing by true 1H spin diffusion reveals  
  long-range intermolecular distance restraints in ultra high magnetic field. J Magn  
  Reson 157: 286-291 
Ernst RR, Bodenhausen G and Wokaun A (1987) Principles of Nuclear Magnetic  
  Resonance in One and Two Dimensions. Clarendon Press, Oxford 
Hartmann SR and Hahn EL (1962) Nuclear double resonance in the rotating frame.  
  Phys Rev 128: 2042 
Lee M and Goldburg WI (1965) Nuclear-magnetic-resonance line narrowing by a  
  rotating rf field. Phys Rev A 140: 1261 
Mehring M (1983) Principles of High Resolution NMR in Solids. Springer-Verlag, Berlin 
Mulder FM, Heinen W, van Duin M, Lugtenburg J and de Groot HJM (1998) Spin   
  diffusion with C-13 selection and detection for the characterization of morphology in  
  labeled polymer blends with MAS NMR. J Am Chem Soc 120: 12891-12894 
Schulten EAM, van Rossum B-J, Ashurst J, Oschkinat H, Raap J, Lugtenburg J and de  
  Groot HJM (1998) Two-dimensional (1H-13C) solid state MAS NMR of isotope  
  labelled chlorophyll a. In: Garab G (ed) Photosynthesis: Mechanisms and Effects, pp  
  453-456. Kluwer Academic Publishers, Dordrecht, the Netherlands 
van Rossum BJ, Forster H and de Groot HJM (1997) High-field and high-speed CP-MAS  
 8
  C-13 NMR heteronuclear dipolar-correlation spectroscopy of solids with frequency-  
  switched Lee-Goldburg homonuclear decoupling. J Magn Reson 124: 516-519 
van Rossum BJ, de Groot CP, Ladizhansky V, Vega S and de Groot HJM (2000) A  
  method for measuring heteronuclear (H-1-C-13) distances in high speed MAS NMR. J  
  Am Chem Soc 122: 3465-3472 
van Rossum BJ, Schulten EAM, Raap J, Oschkinat H and de Groot HJM (2002) A 3-D  
  structural model of solid self-assembled chlorophyll a/H2O from multispin labeling and  
  MAS NMR 2-D dipolar correlation spectroscopy in high magnetic field. J Magn Reson  
  155: 1-14 
Vinogradov E, Madhu PK and Vega S (1999) High-resolution proton solid-state NMR  
  spectroscopy by phase-modulated Lee-Goldburg experiment. Chem Phys Lett 314:  
  443-450 
Wilhelm M, Feng H, Tracht U and Spiess HW (1998) 2D CP/MAS C-
13 isotropic chemical shift correlation established by H-1 spin diffusion. 
J Magn Reson 134: 255-260
 9
Table S1. 13C and 1H chemical shifts, referenced to TMS (δC, H) and 
aggregation shiftsa (ΔδC, H) for Chl a/H2O. The estimated errors for the 
solid state shifts are given in parenthesis. 
 
Position  δC (ppm) ΔδC (ppm) δH (ppm) ΔδH (ppm) 
121 10.5 (0.3) -2.1 -1.3 (0.3) -4.9 
21  10.2 (0.2) -2.4 -2.1 (0.3) -5.4 
71  8.9 / 11.5 (0.2) -2.3 / 0.3 1.7 / 2.8 (0.3) -1.6 / -0.5 
P17  17.4 (0.1) 1.2 1.5 (0.5) 0.0 
82  16.5 / 17.5 (0.5) -1.5 / -0.5 1 (1) -0.7 
81  19.0 / 20.5 (0.5) -1.0 / 0.5 2 (2) -2 
P18  20.0 (0.2) 0.0 0.9 (0.5) 0.1 
P19  20.0 (0.2) 0.0 0.9 (0.5) 0.1 
P20  23.3 (0.3) 0.3 1 (1) 0.2 
P16  23.3 (0.3) 0.3 1 (1) 0.2 
181  24.9 (0.1) 1.0 1.4 (0.5) -0.4 
P9  25.6 (0.3) 0.4 1.2 (0.5) 0.0 
P13  25.6 (0.3) 0.0 1.2 (0.5) 0.0 
P5  25.8 (0.2) 0.0 1.2 (0.5) 0.0 
P15  28.4 (0.2) -0.3 1.3 (0.5) -0.2 
171  32.3 (0.1) 2.2 / 1.3 b 3.0 (0.5) 0.5 
172 32.3 (0.1) 2.2 / 1.3 b 3.0 (0.5) 1.0 
P7  33.1 (0.1) -0.3 1.2 (0.5) -0.1 
P11  33.1 (0.1) -0.5 1.2 (0.5) -0.1 
P6  37.1 (0.5) -0.3 1.0 (0.5) -0.1 
P12  38.0 (0.2) 0.0 1.1 (0.5) 0.0 
P8  38.0 (0.2) 0.0 1.1 (0.5) 0.0 
P10  38.0 (0.2) 0.0 1.1 (0.5) 0.0 
P14  40.0 (0.2) -0.1 2.0 (0.5) 0.9 
P4  40.0 (0.2) -0.4 2.0 (0.5) 0.2 
 10
18  50.0 (0.1) 0.0 2.8 (0.5) -1.8 
17  51.7 (0.3) 0.1 3.9 (0.5) -0.3 
134  51.8 (0.1) -0.2 3.4 (0.5) -0.4 
P1  61.7 (0.1) 0.4 4.9 (0.3) 0.6 
132  64.9 (0.1) -1.3 5.8 (0.5) -0.4 
20  92.6 (0.2) -0.2 6.7 (0.3) -1.9 
5  98.3 (0.1) -1.7 8.6 (0.3) -0.8 
15 103.0 (0.1) -3.2   
10 108.1 (0.1) 1.0 7.8 (0.3) -1.9 
32 113.7 (0.1) -5.2 2.3 (0.5) -3.9 / -3.7 
P2 121.3 (0.1) 1.9 6.0 (0.3) 1.0 
13 126.1 (0.1) -5.4   
31 126.7 (0.1) -4.8 5.7 (0.3) -2.4 
7 132.2 / 133.3 (0.1) -1.8/-0.7   
12 133.0 (0.1) -1.2   
2 135.6 (0.1) 0.1   
3 136.3 (0.1) -2.7   
P3 138.5 (0.1) -3.7   
8 145.4 (0.1) 1.3   
9/11  147.0 (0.1) 0.9/-0.7 b   
4 150.7 (0.1) 2.7   
6 154.1 (0.2) 2.7   
16 154.0 (0.1) -1.8   
1 156.1 (0.1) 2.1   
14 162.3 (0.1) 0.9   
19 169.4 (0.3) 2.0   
133 169.9 (0.1) -1.1   
173 174.3 (0.3) 1.6   
131 190.6 (0.1) 1.3   
 11
a Calculated by substracting the corresponding 1H and 13C shifts for 
monomeric Chl a in acetone-d6, which were obtained from Van Rossum 
(2002) and sources cited therein. 
b The differences between 9-C/11-C, and between 171-C/172-C are not 
resolved in solution. 
 12
Table S2. 13C and 1H chemical shifts, referenced to TMS (δC, H) and 
aggregation shifts (ΔδC, H) for BChl c. The estimated errors for the solid 
state shifts are given in parenthesis.  
 
Position  δC (ppm)a ΔδC  (ppm)a δH (ppm)b ΔδH (ppm)c 
71 10.4 / 6.6 (0.3) 0 / -4.2 3.1 / -0.5 
(0.3) 
0 / -3.7 
F71 16 (1) 0 1.2 (0.6) 0 
F31 16 (1) 0 1.2 (0.6) 0 
122 16.8 (0.6) 0 2 (2) 0 
21 13.8 (0.7) -2.5 1.1 (0.3) -2.2 
82 16.9 (0.6) -0.5 2 (2) 0 
F111 16.6 (0.6) -0.5 1.5 (1) 0 
81 19 (1) 0 2 (2) -2 
181 21 (1) -1 2 (1) 0 
121 17.5 (0.6) -3.5 2 (1) -2 
201 20 (1) -1 3 (1) -1 
F12 25.2 (0.3) 0 1.2 (0.6) 0 
32 22.7 (0.3) -3 1.0 (0.6) -1 
F9 25.7 (0.4) 0 2.0 (0.3) 0 
F5 25.7 (0.4) 0 2.0 (0.3) 0 
171 30 (2) 0 1.4 (0.3) -0.7 
172 30 (2) 0 1.4 (0.3) -1.0 
F8 39.1 (0.3) 0 1.8 (0.3) 0 
F4 39.1 (0.3) 0 1.8 (0.3) 0 
18 48.1 (0.4) 0 4 (1) -1 
132 48.1 (0.4) 0 4.5 (0.6) -0.6 
17 49.7 (0.4) 0 4 (1) 0 
F1 60.9 (0.3) 0 4.5 (0.3) 0 
31 63.7 (0.7) -1 3.0 (0.5) -3.3 
5 101.2 / 95.1 (0.3) -4.5 7.5 / 8.4 (0.3) -2.1 / -1.2 
 13
20 105.0 / 103.5 (0.3) 0   
15 104.3 (0.7) -0.5   
10 105.5 (0.5) 0 10.0 (0.3) 0.6 
F2 119.1 (0.3) 1.5 5.4 (0.3) 0 
F6 124 (1) 0 5.0 (0.3) 0 
F10 124.0 (1.0) 0 5.0 (0.3) 0 
13 127.9 (0.5) -2.5   
F11 130.2 (0.3) -1   
7 132.3 / 131.3 (0.3) -1.5 / -2.5   
F7 135 (1) 0   
2 135.2 (0.3) 0   
12 139 (1) -2   
F3 140.1 (0.3) -1.5   
8 142.1 / 140.1 (0.3) 0 / -2.5   
3 139 (1) -5   
4 143.5 / 144.4 (0.3) -1.8 / -0.9   
9 146.1 / 146.8 (0.3) 0, 0   
11 146.8 (0.4) 0   
6 149.8 / 150.5 (0.3) -0.8 / 0   
1 153.2 (0.5) 0   
16 153.6 (0.5) 0   
14 162.1 (0.3) -1   
19 169.0 / 166.7 (0.3) 1.2 / -1.1   
173 173.0 (0.5) -1   
131 195.8 (0.3) -2.5   
a Values taken from Balaban (1995) and Van Rossum (2001) for the doubled signals. b 
Values taken from Van Rossum (2001). c Calculated from the data given in Van Rossum 
(2001). 
 14
Figure caption 
 
Fig. S1. (A) Pulse sequence of the 2D 13C-13C MAS NMR radio frequency-driven dipolar 
recoupling homonuclear correlation experiment. Following a cross polarization (CP) step, 
the 13C spins precess freely during t1, while heteronuclear decoupling (DEC) is applied on 
the 1H spins. Subsequently, the 13C-13C couplings averaged by MAS are reintroduced by 
a rotor-synchronized train of 180° pulses. During t2 the 13C free induction decay is 
detected. (B) Pulse sequence of the 2D 1H-13C MAS NMR LG-CP heteronuclear 
correlation experiment. After 1H excitation, the 1H spins precess under homonuclear Lee-
Goldburg (LG) decoupling during t1. Subsequently, a CP step forms the mixing interval 
and the 13C free induction decay is detected in t2. 


https://epub.ub.uni-muenchen.de/776/5/Chapter_20_DeBoer_DeGrootSupplement.pdf

Chlorophylls and Bacteriochlorophylls: Biochemistry, Biophysics, Functions and Applications

Abstract

Similar works

Full text

Available Versions

Open Access LMU

Universität München: Elektronischen Publikationen