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Solid-State 1H, 13C, and 17O NMR Characterization of the Two Uncommon Polymorphs of Curcumin
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    Solid-State 1H, 13C, and 17O NMR Characterization of the Two Uncommon Polymorphs of Curcumin
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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2020, 20, 11, 7484–7491
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    https://doi.org/10.1021/acs.cgd.0c01164
    Published October 14, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    Curcumin is known to exist in three polymorphs (forms I, II, and III) in the solid state. The most common polymorph of curcumin (form I) is monoclinic in the space group P2/n, whereas the other two uncommon forms are both orthorhombic with the space groups of Pca21 and Pbca for forms II and III, respectively. While crystal structures are known for all three polymorphs of curcumin, their solid-state NMR signatures are incomplete in the literature. In this study, we report a complete set of solid-state 1H, 13C, and 17O NMR data for form III of curcumin. In addition, we discovered that form III of curcumin prepared by repeated drying from methanol is not stable, which undergoes slow structural transition to form II in the solid state over a period of days at room temperature. As a result, we were able to obtain new solid-state 17O NMR data for form II of curcumin, which complements the existing solid-state 1H and 13C NMR data for this polymorph in the literature. We compare experimental NMR parameters with calculated values by the GIPAW DFT and dispersion corrected DFT-D2 methods. We found that while the computed 13C chemical shifts are generally in excellent agreement with experimental values, the quality of the computed 1H and 17O NMR chemical shifts is less satisfactory. This may imply that it is necessary to include the nuclear quantum effects in future quantum chemical calculations to account for potential proton tunneling and dynamics.

    Copyright © 2020 American Chemical Society

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    • 1H MAS NMR spectra showing the conversion from form I to form III. Stability of form III crystals monitored by 13C CP/MAS NMR. 17O MAS spectrum of form III obtained at 21.1 T. Computational results from DFT-D2. A complete list of computed 1H and 13C chemical shifts. (PDF)

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    This article is cited by 12 publications.

    1. Gang Wu, Yizhe Dai, Ivan Hung, Zhehong Gan, Victor Terskikh. 1H/17O Chemical Shift Waves in Carboxyl-Bridged Hydrogen Bond Networks in Organic Solids. The Journal of Physical Chemistry A 2024, 128 (21) , 4288-4296. https://doi.org/10.1021/acs.jpca.4c01866
    2. Beibei Lu, Jianglin Zhang, Jiaheng Zhang. Enhancing Transdermal Delivery of Curcumin-Based Ionic Liquid Liposomes for Application in Psoriasis. ACS Applied Bio Materials 2023, 6 (12) , 5864-5873. https://doi.org/10.1021/acsabm.3c01026
    3. Xuxing Wan, Yifu Chen, Yuechao Cao, Zhenguo Gao, Songgu Wu, Junbo Gong. Reversible Intramolecular Proton Transfer in Curcumin Crystals and Nonlinear Size Correlation. Crystal Growth & Design 2023, 23 (7) , 5025-5034. https://doi.org/10.1021/acs.cgd.3c00255
    4. Valeria A. Stepanova, Andres Guerrero, Cullen Schull, Joshua Christensen, Claire Trudeau, Joshua Cook, Kyle Wolmutt, Jordan Blochwitz, Abdelrahman Ismail, Joseph K. West, Amelia M. Wheaton, Ilia A. Guzei, Bin Yao, Alena Kubatova. Hybrid Synthetic and Computational Study of an Optimized, Solvent-Free Approach to Curcuminoids. ACS Omega 2022, 7 (8) , 7257-7277. https://doi.org/10.1021/acsomega.1c07006
    5. Daria Torodii, Jacob B. Holmes, Pinelopi Moutzouri, Sten O. Nilsson Lill, Manuel Cordova, Arthur C. Pinon, Kristof Grohe, Sebastian Wegner, Okky Dwichandra Putra, Stefan Norberg, Anette Welinder, Staffan Schantz, Lyndon Emsley. Crystal structure validation of verinurad via proton-detected ultra-fast MAS NMR and machine learning. Faraday Discussions 2025, 255 , 143-158. https://doi.org/10.1039/D4FD00076E
    6. Phuong-Truc T. Pham, Mamoun M. Bader. α-Halogenated Curcumins. Crystals 2024, 14 (12) , 1041. https://doi.org/10.3390/cryst14121041
    7. Giulia Del Duca, Emmanuele Parisi, Fiora Artusio, Eleonora Calì, Silvia Fraterrigo Garofalo, Chiara Rosso, Valentina Cauda, Michele Remo Chierotti, Elena Simone. A crystal engineering approach for rational design of curcumin crystals for Pickering stabilization of emulsions. Food Research International 2024, 224 , 114871. https://doi.org/10.1016/j.foodres.2024.114871
    8. Yizhe Dai, Victor Terskikh, Gang Wu. A combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds. Solid State Nuclear Magnetic Resonance 2024, 132 , 101945. https://doi.org/10.1016/j.ssnmr.2024.101945
    9. Chia‐Hsin Chen, Ieva Goldberga, Philippe Gaveau, Sébastien Mittelette, Jessica Špačková, Chuck Mullen, Ivan Petit, Thomas‐Xavier Métro, Bruno Alonso, Christel Gervais, Danielle Laurencin. Looking into the dynamics of molecular crystals of ibuprofen and terephthalic acid using 17 O and 2 H nuclear magnetic resonance analyses. Magnetic Resonance in Chemistry 2021, 59 (9-10) , 975-990. https://doi.org/10.1002/mrc.5141
    10. Katia Rubini, Elisa Boanini, Silvia Parmeggiani, Adriana Bigi. Curcumin-Functionalized Gelatin Films: Antioxidant Materials with Modulated Physico-Chemical Properties. Polymers 2021, 13 (11) , 1824. https://doi.org/10.3390/polym13111824
    11. Marta K. Dudek, Sławomir Kaźmierski, Marek J. Potrzebowski. Fast and very fast MAS solid state NMR studies of pharmaceuticals. 2021, 97-189. https://doi.org/10.1016/bs.arnmr.2021.02.002
    12. James Palmer, Gang Wu. Recent developments in 17O NMR studies of organic and biological molecules in the solid state. 2021, 1-46. https://doi.org/10.1016/bs.arnmr.2021.03.001

    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2020, 20, 11, 7484–7491
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.cgd.0c01164
    Published October 14, 2020
    Copyright © 2020 American Chemical Society

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