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Solid-state ¹H, ¹³C, and ¹⁷O NMR characterization of the two uncommon polymorphs of curcumin

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S1

Supporting Information

Solid-state

1

H,

13

C,

17

O NMR characterization of the two

uncommon polymorphs of curcumin

Yizhe Dai,1 Victor Terskikh,1,2 Andreas Brinmkmann,2 and Gang Wu1*

1Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario,

Canada K7L 3N6;

2Metrology, National Research Council Canada, 1200 Montreal Road, Ottawa, Canada

K1A 0R6.

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S2

Figure S1. 1H MAS NMR spectra of curcumin samples at different stages of the

preparation for form III. (a) After quickly drying from a MeOH solution with a stream of N2(g). (b) After another dissolution/drying cycle from (a). (c) Two more

dissolution/drying cycles from (b). All 1H MAS spectra were recorded at 16.4 T (700 MHz for 1H) with a sample spinning frequency of 30 kHz. The sample temperature was

controlled at 293 K. δ(10 1H)/ppm 5 0 -5 15 20 25 Form I Form III

(a)

(b)

(c)

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Figure S2. 13C CP/MAS NMR spectra showing the stability of the form-III curcumin

crystals. All spectra were recorded at 16.4 T (700 MHz for 1H and 176 MHz for 13C) with a sample spinning frequency of 20 kHz. The sample temperature was controlled at 293 K.

δ(13C)/ppm 100 50

150 200

Freshly made 6 months later

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Figure S3. Experimental (black traces) and simulated (colored traces) 17O MAS NMR

spectra of a form-II curcumin sample recorded at 21.1 T (900 MHz for 1H and 122 MHz for 17O) with a sample spinning frequency of 22 kHz. The sample temperature was controlled at 293 K.

δ(17O)/ppm 200 100 0

300 400

O1B O1A O2A O2B

exp

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Figure S4. Comparison between experimental and computed 1H, 13C, and 17O chemical

shifts for the three polymorphs of curcumin. The diagonal line is shown to aid for visual inspection of data. The inset shows the expanded region around the 1H chemical shift data points. All calculations were done with dispersion corrected DFT-D2. Data points that deviate from the diagonal line are highlighted.

0 50 100 150 200 250 300 350 400 0 100 200 300 400 C o m p u te d c h em ic al s h ift/ p p m

Experimental chemical shift/ppm

1H 13C 17O Form-I Form-II-Mol-A 10 12 14 16 18 20 10 12 14 16 18 20 Form-I

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Table S1. Complete list of computed 13C and 1H chemical shifts for curcumin in Form

III.

Atom CASTEP σiso/ppm δiso/ppm

C1 C15 16.71 153.7 C2 C3 19.26 151.1 C3 C2 51.79 118.6 C4 C1 43.31 127.1 C5 C14 50.21 120.2 C6 C16 50.55 119.9 C7 C7 27.40 143.0 C8 C5 43.47 126.9 C9 C9 -15.56 186.0 C10 C4 59.67 110.7 C11 C6 -7.29 177.7 C12 C8 50.16 120.2 C13 C11 26.67 143.7 C14 C10 40.59 129.8 C15 C12 51.58 118.8 C16 C21 54.84 115.6 C17 C13 17.20 153.2 C18 C19 19.61 150.8 C19 C18 53.98 116.4 C20 C20 112.42 68.0 C21 C17 113.23 57.2 H1 H19 19.8 9.2 H3 H1 24.29 4.7 H4A H18 13.54 15.5 H5 H8 23.72 5.3 H5A H20 22.90 6.1 H6 H9 23.73 5.3 H7 H4 24.57 4.4 Form3 Curcumin Page 1 f a b Comment 0.50 -1.0000 170.4000 Gang Wu -1.0000 29.0000 Gang Wu -1.0000 287.0000 Gang Wu

Parameters: σcalc = a δexp + b

13C 1H 17O

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S7 H8 H3 24.75 4.3 H10 H2 25.09 3.9 H12 H5 23.81 5.2 H13 H6 24.02 5.0 H15 H7 23.41 5.6 H16 H17 23.45 5.6 H19 H13 24.59 4.4 H20A H14 26.54 2.5 H20B H15 26.45 2.6 H20C H16 27.46 1.5 H21A H10 25.95 3.1 H21B H11 26.97 2.0 H21C H12 28.16 0.8

Figure

Figure  S1.  1 H  MAS  NMR  spectra  of  curcumin  samples  at  different  stages  of  the  preparation for form III
Figure  S2.  13 C  CP/MAS  NMR  spectra  showing  the  stability  of  the  form-III  curcumin  crystals
Figure  S3.  Experimental  (black  traces)  and  simulated  (colored  traces)  17 O  MAS  NMR  spectra of a form-II curcumin sample recorded at 21.1 T (900 MHz for  1 H and 122 MHz  for  17 O)  with  a  sample  spinning  frequency  of  22  kHz
Figure S4. Comparison between experimental and computed  1 H,  13 C, and  17 O chemical  shifts for the three polymorphs of curcumin
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