www.sciencemag.org/content/347/6222/646/suppl/DC1

Supplementary Materials for

A rational strategy for the realization of chain-growth supramolecular

polymerization

Jiheong Kang, Daigo Miyajima,* Tadashi Mori, Yoshihisa Inoue, Yoshimitsu Itoh,

Takuzo Aida*

*Corresponding author. E-mail: daigo.miyajima@riken.jp (D.M.); aida@macro.t.u-tokyo.ac.jp (T.A.)

Published 6 February 2015, Science 347, 646 (2015)

DOI: 10.1126/science.aaa4249

This PDF file includes:

Materials and Methods

Supplementary Text

Figs. S1 to S27

Tables S1 to S3

Full Reference List

S1  

Supplementary Material

A Rational Strategy for the Realization of Chain-Growth Supramolecular Polymerization

Jiheong Kang, Daigo Miyajima,* Tadashi Mori, Yoshihisa Inoue, Yoshimitsu Itoh,

and Takuzo Aida*

* To whom correspondence should be addressed.

E-mail: daigo.miyajima@riken.jp (D.M.); aida@macro.t.u-tokyo.ac.jp (T.A.)

Table of Contents

1. General .................................................................................................................................. S2

2. Synthesis of Compounds ...................................................................................................... S3

3. Analytical Data .................................................................................................................... S5

4. Supplementary Methods .................................................................................................. S10

5. Supplementary Figures ...................................................................................................... S14

6. References ........................................................................................................................... S33

  S2  

1. General

Unless otherwise noted, all commercial reagents were used as received. 1H and 13C NMR spectra

were recorded at 25 °C on a JEOL model JNM-ECA500 spectrometer, operating at 500 and 125

MHz, respectively, where chemical shifts (δ in ppm) were determined using tetramethylsilane (δ

0.0 ppm) for 1H NMR and CDCl3 (δ 77.1 ppm) for 13C NMR as internal references. Matrix-

assisted laser desorption ionization time-of-flight (MALDI–TOF) mass spectrometry was

performed in the reflector mode on a Brucker model autoflex TM speed spectrometer. Electronic

absorption and circular dichroism (CD) spectra were recorded on a JASCO model V-670

UV/VIS/NIR spectrophotometer and a JASCO Type J-820 spectropolarimeter, respectively,

using a quartz cell of 10 mm optical path length. Dynamic light scattering (DLS) measurements

were performed with a Malvern type Zetasizer Nano ZSP at 25 °C using a quartz cell of 10 mm

optical path length. Fourier-transform infrared (FT-IR) spectra were recorded using a JASCO

model FT/IR-610Plus infrared spectrometer. Vibrational circular dichroism (VCD) spectra were

measured in a 0.5-mm thick BaF2 cell with a JASCO model FVS-6000 spectrometer. All VCD

spectra were collected for ca. 4 h (6000-time accumulation) with a resolution of 4 cm–1.

Analytical size-exclusion chromatography (SEC) was performed at 4 °C, using a TSKgel Super

Multipore Hz-M column on a JASCO Type PU-2080i Plus equipped with a JASCO Type MD-

2015 Plus variable-wavelength UV-Vis detector and a JASCO Type CD-2095A variable-

wavelength CD detector. Number-average molecular weights (Mn) and weight-average molecular

weights (Mw) were calculated relative to linear polystyrene standards. Tapping-mode atomic

force microscopy (AFM) images of polymerized mixtures were recorded by an Asylum Research

type CypherS AFM microscope, where all samples were prepared by drop-casting and air-drying

on silicon wafer after 100-fold dilution (0.01 mM).

  S3  

2. Synthesis of Compounds

Compounds M, MR, and MS were synthesized and unambiguously characterized (18).

I: To a THF solution (5 mL) of M (500 mg, 3.6 mol), chilled with an ice bath, was slowly added

a NaH THF solution (1 M, 5 mL) over a period of 5 min, and the mixture was stirred for 0.5 h at

20 °C. CH3I (0.5 mL, 6.0 mol) was added to the resulting solution, and the mixture was refluxed

for 18 h at 80 °C. Then, water was slowly added to the resulting solution, and the mixture was

extracted twice with CH2Cl2 (10 mL). An organic extract separated was dried over Mg2SO4 and

evaporated to dryness under reduced pressure. The residue was chromatographed on silica gel

with hexane/AcOEt (1/1 v/v) as an eluent, where the first fraction was collected and evaporated to

dryness under reduced pressure to give I as yellow waxy solid (492 mg, 74%). 1H NMR (500

MHz, CDCl3) δ (ppm) 7.45 (s, 5H), 3.76 (m, 10H), 3.42-3.22 (m, 25H), 2.53 (t, J = 7.7 Hz, 10H),

1.86 (m, 10H), 1.31 (t, J = 8.5 Hz, 10H), 1.30 (m, 40H), 0.83 (t, J = 6.9 Hz, 10H); 13C NMR (125

MHz, CDCl3) δ (ppm) 174.5, 135.6, 131.3, 128.7, 118.7, 38.7, 36.5, 33.6, 31.5, 29.4, 28.9, 25.8,

RR

R

RR

S NH

O

RR

R

RR

S NH

OR

R

R

RR

S NH

O

R =

R =

R =

M

MS

RR

R

RR

S NO

RR

R

RR

S NO

RR

R

RR

S NO

R =

R =

R =

I

IR

Me

Me

Me

NaH CH3I

THF

NaH CH3I

THF

NaH CH3I

THF

MR

  S4  

22.3, 13.7. MALDI-TOF mass, m/z calculated for compound I [M + Na]+; 1418.83, found;

1419.35.

IR: Compound IR was likewise derived from MR. 1H NMR (500 MHz, CDCl3) δ (ppm) 7.45 (s,

5H), 3.76 (m, 10H), 3.40 (m, 25H), 2.51 (dd, J = 5.1 and 14.0 Hz, 5H), 2.29 (dd, J = 8.6 and 14.0

Hz, 5H), 2.15 (m, 5H), 1.41 (m, 30H), 1.22 (m, 10H), 1.08 (d, J = 6.2 Hz, 15H), 0.83 (d, J = 6.4

Hz, 30H); 13C NMR (125 MHz, CDCl3) δ (ppm) 174.2, 135.4, 131.9, 129.0, 120.4, 44.3, 39.3,

39.1, 37.6, 34.2, 30.8, 28.1, 25.0, 22.5, 22.6, 20.3. MALDI-TOF mass, m/z calculated for

compound IR [M + Na]+; 1558.98, found; 1559.99.

IS: Compound IS was likewise derived from MS. 1H NMR (500 MHz, CDCl3) δ (ppm) 7.42 (s,

5H), 3.76 (m, 10H), 3.40 (m, 25H), 2.51 (dd, J = 5.1 and 14.0 Hz, 5H), 2.29 (dd, J = 8.6 and 14.0

Hz, 5H), 2.15 (m, 5H), 1.41 (m, 30H), 1.22 (m, 10H), 1.08 (d, J = 6.2 Hz, 15H), 0.83 (d, J = 6.4

Hz, 30H); 13C NMR (125 MHz, CDCl3) δ (ppm) 174.1, 134.9, 131.4, 128.1, 120.7, 43.1, 39.3,

39.3, 37.4, 34.7, 31.0, 28.0, 25.3, 22.7, 22.3, 21.0. MALDI-TOF mass, m/z calculated for

compound IS [M + Na]+; 1558.98, found; 1559.44.

  S5  

3. Analytical Data

3.1 1H and 13C NMR Spectroscopy

Fig. S1. 1H NMR spectrum (500 MHz) of I in CDCl3 at 25 °C.

PPM

175 150 125 100 75 50 25 0

DFILE \\Aida-nmr\550nmr\zhihua\20110430_5tikan_S_C7rev_500_VT55_13C(edit).alsCOMNTDATIM Sat Apr 30 11:52:11 2011OBNUC 13CEXMOD SINGLOBFRQ 125.65 MHzOBSET 0.00 KHzOBFIN 127958.00 HzPOINT 32768FREQU 33898.30 HzSCANS 1942ACQTM 0.9667 secPD 1.0000 secPW1 5.00 usecIRNUC 1HCTEMP 55.0 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 28

\\Aida-nmr\550nmr\zhihua\20110430_5tikan_S_C7rev_500_VT55_13C(edit).als

174.

514

135.

583

131.

215

128.

328

119.

000

38.

603

36.

530

33.

635

31.

521

29.

431

28.

897

25.

829

22.

349

13.

688

!ppm180 150 120 90 60 30 0

Fig. S2. 13C NMR spectrum (125 MHz) of I in CDCl3 at 25 °C.

  S6  

Fig. S3. 1H NMR spectrum (500 MHz) of IR in CDCl3 at 25 °C.

PPM

175 150 125 100 75 50 25

DFILE \\Aida-nmr\550nmr\harada\20110502_5tikanS-C7rev_minus_VT55_500_13C(edit).alsCOMNTDATIM Mon May 02 20:09:09 2011OBNUC 13CEXMOD SINGLOBFRQ 125.65 MHzOBSET 0.00 KHzOBFIN 127958.00 HzPOINT 32768FREQU 33898.30 HzSCANS 2000ACQTM 0.9667 secPD 1.0000 secPW1 5.00 usecIRNUC 1HCTEMP 54.9 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 27

\\Aida-nmr\550nmr\harada\20110502_5tikanS-C7rev_minus_VT55_500_13C(edit).als

174.

054

135.

764

131.

931

129.

010

120.

431

77.

255

77.

000

76.

745

44.

435

39.

286

39.

022

37.

492

34.

161

30.

739

27.

984

24.

874

22.

637

22.

538

20.

161

!ppm180 150 120 90 60 30 0

Fig. S4. 13C NMR spectrum (125 MHz) of IR in CDCl3 at 25 °C.

  S7  

Fig. S5. 1H NMR spectrum (500 MHz) of IS in CDCl3 at 25 °C.

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㪈㪎㪊㪅㪐㪇㪌

㪈㪊㪌㪅㪍㪋㪍

㪈㪊㪈㪅㪎㪋㪎

㪈㪉㪏㪅㪏㪌㪇

㪈㪉㪇㪅㪉㪎㪎

㩷㪋㪋㪅㪋㪎㪍

㩷㪊㪐㪅㪊㪋㪉

㩷㪊㪐㪅㪇㪐㪌

㩷㪊㪎㪅㪌㪌㪎

㩷㪊㪋㪅㪉㪉㪌

㩷㪊㪇㪅㪏㪈㪏

㩷㪉㪏㪅㪇㪎㪇

㩷㪉㪋㪅㪐㪍㪇

㩷㪉㪉㪅㪎㪊㪈

㩷㪉㪉㪅㪍㪊㪉

㩷㪉㪇㪅㪉㪍㪉

㩷㩷㪈㪅㪈㪋㪈

!ppm180 150 120 90 60 30 0

Fig. S6. 13C NMR spectrum (125 MHz) of IS in CDCl3 at 25 °C.

  S8  

3.2 MALDI-TOF Mass Spectrometry

Fig. S7. MALDI-TOF mass spectrum of I using CHCA as a matrix.

1500 16001400130012001100 1700 1800 1900 2000m/z

1559.99

Fig. S8. MALDI-TOF mass spectrum of IR using CHCA as a matrix.

1500 16001400130012001100 1700 1800 1900 2000

1419.35

m/z

  S9  

Fig. S9. MALDI-TOF mass spectrum of IS using CHCA as a matrix.

1500 16001400130012001100 1700 1800 1900 2000

1559.44

m/z

  S10  

4. Supplementary Methods

Preparation of Monomeric Samples of M, MR, and MS in MCHex

Typically, a mixture of M and its polymers (14 mg, 1.0 mmol) was dissolved in CHCl3 (5 mL),

and the resulting solution was slowly evaporated to dryness with gentle stirring at room

temperature under reduced pressure. The residue was then dissolved in MCHex

(methylcyclohexane, 10 mL) upon sonication with an ice bath. By this procedure, molecularly

dispersed M employed for the chain-growth supramolecular polymerization was obtained, as

confirmed by SEC-UV and DLS. MCHex solutions of molecularly dispersed MR and MS were

likewise prepared.

Thermal Polymerization of M without I

A MCHex solution of M ([M] = 1.0 mM) was heated at 60 °C for 12 h and then allowed to cool

to 25 °C and stand for 12 h. The formation of polymeric M at the complete monomer

consumption was confirmed by SEC-UV (see Fig. S12).

Size-Exclusion Chromatography (SEC)

All analytical SEC measurements were performed at 4 °C with CHCl3/MCHex (1/1 v/v) as an

eluent, monitored by UV and CD detectors at 290 nm. An analyte (10 µL) was slowly injected

into the sample injection loop. Number-average (Mn) and weight-average molecular weights

(Mw) were estimated using a calibration curve based on polystyrene standards. The flow rate was

set at 0.5 mL min–1, whereas that for the SEC in Fig. 3D was 0.2 mL min–1.

  S11  

*Note: Although polymeric M, MR, and MS dissociate into their monomers in CHCl3, they are

sufficiently stable in CHCl3/MCHex (1/1 v/v) at 4 °C (Fig. S27). Therefore, SEC was carried out

using CHCl3/MCHex (1/1 v/v) as eluent at 4 °C.

Evaluation of the Degrees of Polymerization (Dp) of Polymers by DOSY NMR

According to the Stokes-Einstein relation (eq. 1), the diffusion coefficient (D) of a molecule is

inversely proportional to its hydrodynamic radius R, where kB, T, and η are Boltzmann constant,

temperature, and dynamic viscosity of the solvent, respectively.

D = kBT/6πηR ------------------- eq. 1

As summarized in Figs. 2B and S10, the diffusion coefficients (D) of polymeric M at varying

[M]0/[I]0 ratios, together with that of monomeric M, were obtained at 293 K by DOSY NMR

experiments in deuterated MCHex at [M]0 = 1.0 x 10−4 M (21). With these D values, the Dp

values of the polymers were estimated by eq. 2.

DP = (D of monomeric M)3/(D of polymeric M)3 ------------------- eq. 2

The Dp values thus estimated are a rough approximation because the theoretical treatment

involves an assumption that a polymer is hydrodynamically spherical. Nevertheless, the Dp

values are in good agreement with the number-averaged Dp values expected from [M]0/[I]0.

  S12  

Evaluation of %-Enantiomeric Excess of Polymeric M

In a previous paper (18), we estimated (31–33) that molar ellipticities ([θ]) of the C5-symmetirc

chiral corannulene skeleton of MR in MCHex at 25 °C are [θ]290 = 7.0 × 104 deg cm2 dmol–1, [θ]337

= 2.9 × 104 deg cm2 dmol–1, and [θ]378 = –2.8 × 104 deg cm2 dmol–1 at 290, 337, and 378 nm,

respectively. By using these values and eq. 3, the %-enantiomeric excesses of polymeric M in

MCHex at 25 °C were estimated based on its apparent molar ellipticities (app[θ]) observed at 290,

337, and 378 nm and summarized in Tables S2 and S3.

%-Enantiomeric Excess = 100 × (app[θ]/[θ]) ------------------- eq. 3

Structural Optimization of Trimeric M Using Simplified Model M’

All calculations were performed with the Gaussian 09 or Turbomole 6.5 program package (34),

where structural optimizations were carried out at DFT-D3(BJ)-TPSS/def2-TZVP level followed

by frequency calculation at the same level, affording the structures on the next page with zero

imaginary frequencies. For shortening the calculation time, simplified molecular model M’ (A)

was used instead of M. Prior to this, we first calculated dimeric M’ with clockwise and

counterclockwise geometries in regard to the intermolecularly H-bonded amide network (green).

As shown in (B) and (D), when the C5-symmetric corannulene core adopts a clockwise

(counterclockwise) geometry, M’ stacks up to give a stable 1D assembly only when the

intermolecularly H-bonded amide network adopts a clockwise (counterclockwise) geometry.

Namely, the stereochemistry of the chiral corannulene skeleton, once fixed upon dimerization,

unambiguously determines that of the intermolecularly H-bonded amide network. The same held

true when trimeric M’ was calculated (C). This geometrical coherence most likely leads to the

high stereospecificity of the supramolecular polymerization. For the purpose of estimating the

  S13  

VCD spectra in Fig. S21, the geometrically optimized structure of trimeric M’ (C) was

employed.

  S14  

5. Supplementary Figures 5.1. 1H DOSY NMR Spectroscopy of Polymeric M Formed with I in Deuterated MCHex

Fig. S10. 1H DOSY NMR spectra in deuterated MCHex at 20 ºC (500 MHz) of monomeric M (dark red) and its polymers formed at [M]total/[I]0 = 50 (purple), 250 (dark yellow), 500 (green), and 1000 (blue).

  S15  

5.2. AFM Height Image Analysis of Polymeric M Formed with I

Fig. S11. Height images of tapping-mode AFM micrographs and their cross-sectional profiles on silicon wafer of air-dried samples of polymerized mixtures of M formed with I at [M]total/[I] = (A) 50, (B) 250, (C) 500, (D) 1000, (E) 2000, and (F) 4000.

  S16  

5.3. SEC Characterization of Polymeric M Formed Thermally or with I

Fig. S12. SEC-UV trace at 290 nm of polymeric M formed with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C (black) and that of a thermally polymerized reference ([M]0 = 1.0 mM) in MCHex at 60 °C without I (red). A broken line represents the peak-top position of monomeric M.

  S17  

5.4. FT-IR Characterization of Monomeric and Polymeric M

Fig. S13. FT-IR spectra at 25 °C of monomeric M (1.0 mM, blue) and its polymer formed with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM, red) in MCHex at 25 °C. (A) N-H and (B) C=O regions.

  S18  

5.5. Electronic Absorption Spectral Characterization of Monomeric M and Its Polymer

Fig. S14. Electronic absorption spectra in MCHex at 25 °C of monomeric M ([M] = 1.0 mM, black) and its polymer formed with I at [M]0/[I]0 = 500 ([M] = 1.0 mM, red).

  S19  

5.6. Dilution Effects on Polymeric M Studied by SEC

Fig. S15. Polymerization of M initiated with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C. (A) SEC traces of polymeric M before (red) and after dilution to [M] = 0.5 (pink), 0.3 (orange), 0.2 (green), and 0.1 mM (blue). A broken line represents the peak-top position of monomeric M. (B) Plots of the degrees of polymerization (Dp) and polydispersity indexes (PDI) of polymers from (A) versus [M]. Dp values were estimated using a calibration curve based on polystyrene standards.

  S20  

5.7 Effects of Thermal Annealing on Polymeric M Studied by SEC

Fig. S16. SEC-UV traces at 290 nm of polymerized mixtures of M formed with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C before (black) and after heating at 100 ºC for 1 h and subsequent cooling to 25 ºC at rates of 1.0 °C min–1 (blue) and 20 °C min–1 (red). A broken line represents the peak-top position of monomeric M.

  S21  

5.8. Effects of CHCl3 on Polymeric M Studied by DLS

Fig. S17. DLS profiles of polymerized mixtures of M formed with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C before (red) and after 10-fold dilution with CHCl3 (blue).

  S22  

5.9. Effects of Initiator I on Bimolecular Polymer Recombination Studied by SEC

Fig. S18. SEC-UV traces at 290 nm of a thermally polymerized M ([M] = 1.0 mM) in MCHex at 60 °C. A MCHex solution of thermally polymerized M (A) was divided into two portions and both were sonicated for 1 h at –78 °C (B). While one portion was allowed to stand at 25 °C for 24 h (C), the other was immediately mixed with I (1.0 mM) at [M]0/[I]0 = 5 (D) and then allowed to stand at 25 °C for 24 h (E).

  S23  

5.10. Polymerization of MR (MS) with IR (IS) Studied by CD Spectroscopy

Fig. S19. Time-dependent CD spectra at 25 °C in MCHex of polymeric MR formed with IR at [MR]0/[IR]0 = 500 ([MR]0 = 1.0 mM) in 0 (black), 1 (blue), 2 (cyan), 3 (green), 4 (orange), and 5 h (red). A broken curve represents the CD spectrum of polymeric MS formed with IS in 5 h under conditions otherwise identical to the above.

  S24  

5.11. Polymerizations of M, MR, and MS with IR Studied by CD Spectroscopy

Fig. S20. Time-dependent changes in [θ] at 290 nm ([θ]290) upon mixing IR with M (black), MR (red), and MS (blue) at [monomer]/[IR] = 500 ([monomer] = 1.0 mM) in MCHex at 25 °C.

  S25  

5.12. FT-IR and VCD Characterizations of Polymeric M, MR, and MS

Fig. S21. Experimental VCD (upper) and FT-IR (lower) spectra at 25 °C of (A) polymerized mixtures of M with IR (red) and IS (blue), and (B) those of MR with IR (red) and of MS with IS (blue) in MCHex. (C) Theoretical VCD (upper) and FT-IR (lower) spectra of trimeric M’ adopting a clockwise geometry of corannulenes and a clockwise array of intermolecular H-bonds (blue), and its enantiomeric form (red) obtained by a time-dependent DFT method at B3LYP/6-31g(d) level. The frequencies were scaled with a factor 0.96, and a bandwidth of 6 cm–1 was employed. Note that DFT calculation at DFT-D3(BJ)-TPSS/def2-TZVP level was used for the structural optimization of trimeric M’.

  S26  

5.13. SEC Characterization of Polymeric MS Formed with IS

Fig. S22. SEC-UV trace at 290 nm of polymeric MS formed with IS at [MS]0/[IS]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C.

  S27  

5.14. CD Characterization of Monomeric MR (MS) and Polymeric M Formed with IR (IS)

Fig. S23. CD spectra of monomeric MR (blue solid curve), monomeric MS (blue broken curve), and polymerized mixtures of M with IR (red solid curve) and IS (red broken curve) at [M]0/[initiator]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C.

  S28  

5.15. Effects of Sonication on Polymeric M Studied by CD spectroscopy

Fig. S24. CD spectra of polymeric M formed with IR at [M]0/[IR]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C before (blue) and after sonication at –78 ºC for 1 h (red).

  S29  

5.16. SEC Characterization of Polymerized Mixtures of MR with IR and of Mrac with IR

Fig. S25. SEC-UV (upper) and SEC-CD (lower) traces at 290 nm of (A) polymerized mixtures of Mrac formed with IR at [Mrac]0/[IR]0 = 500 ([Mrac]0 = 1.0 mM) in 6 h (black) and 14 days (red), and (B) those of a polymerized mixture of MR formed with IR at [Mrac]0/[IR]0 = 250 ([MR]0 = 0.5 mM) in 6 h (red) together with those of monomeric MS ([MS]= 0.5 mM) (blue) and black SEC-UV and SEC-CD traces in (A).

  S30  

5.17. DSC Characterization of Monomeric M and Its Polymer

Fig. S26. DSC thermograms of monomeric M (blue) and its thermally formed polymer (red) on first heating at a rate of 10 °C min–1. Samples were prepared by evaporation at 0 °C.

  S31  

5.18. Effects of Incubation on Polymeric M in MCHex/CHCl3 Studied by DLS

Fig. S27. Polymerization of M with I at [M]0/[I]0 = 500 ([M]0 = 1.0 mM) in MCHex at 25 °C. DLS profiles at 4 °C after incubation of the resultant polymer for 0, 1, 2, and 3 h in MCHex/CHCl3 (1/1) at 4 °C.

  S32  

Table S1. Dp and PDI Data of Polymerized Mixtures Aged for 1 day and 30 days

For SEC estimation of Dp and PDI values, a calibration curve based on polystyrene standards

was used. Table S2. Apparent Molar Ellipticities and Estimated Enantiomeric or Diastereomeric Excesses of MR, Polymeric M with IR, and Polymeric MR with IR

Molar ellipticities were evaluated by CD spectroscopy in MCHex at 25 °C.

Table S3. Apparent Molar Ellipticities and Estimated Enantiomeric or Diastereomeric Excesses of MS, Polymeric M with IS, and Polymeric MS with IS

Molar ellipticities were evaluated by CD spectroscopy in MCHex at 25 °C.

S33

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