•  
  •  
 

Corresponding Author

Bao-kang JIN(bkjinhf@aliyun.com)

Abstract

The electrochemical reduction of emodin (Q) has been investigated in acetonitrile by cyclic voltammetry (CV), IR spectroelectrochemistry cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. It was found that anion radical Q•− interacted with neutral Q to form dimer Q2•− which was further reduced to Q22− at more negative potentials. A two-step one-electron process involving electrochemical reductions of Q22− to form Q23− in the first step and Q24− in the second step, corresponding to the two cathodic peaks of C3 and C4 in CV curves was confirmed. When the scan range was between 1.0 and -2.0 V, there were two new anodic peaks (A1, A2) formed at more positive potentials. When the scan range was 0.3~-1.4 V, the current value of A2 increased with the added scan cycles, indicating that Q2•− accumulated in the solution. The C1 and C2 peaks still appeared in the second and third scans in CV curves under the consecutive scans from 1.0 to -2.0 V, suggesting the regainer of Q after each potential cycle. And Q2•− would be oxidized to Q at the potential corresponding to A1. As a result, the electrochemical redox mechanism of emodin has been proposed.

Graphical Abstract

Keywords

emodin, dimerization, in situ FT–IR spectroelectrochemistry, cyclic voltabsorptometry (CVA), derivative cyclic voltaborptometry (DCVA)

Publication Date

2017-06-29

Online Available Date

2016-11-29

Revised Date

2016-11-25

Received Date

2016-10-27

References

[1] Agarwal S, Singh S S, Verma S, et al. Antifungal activity of anthraquinone derivatives from< i> Rheum emodi[J]. Journal of ethnopharmacology, 2000, 72 (1):43-46.

[2] Alves S, Cesar C, F Da Costa C, et al. Synthesis and Evaluation of Cytotoxicity and Inhibitory Effect on Nitric Oxide Production by J774A. 1 Macrophages of New Anthraquinone Derivatives[J]. Medicinal Chemistry, 2013, 9 (6):812-818.

[3] Ly D, Sanii L, Schuster G B. Mechanism of charge transport in DNA: internally-linked anthraquinone conjugates support phonon-assisted polaron hopping[J]. Journal of the American Chemical Society, 1999, 121 (40):9400-9410.

[4] Takahashi E, Marczylo T H, Watanabe T, et al. Preventive effects of anthraquinone food pigments on the DNA damage induced by carcinogens in< i> Drosophila[J]. Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis, 2001, 480:139-145.

[5] Esmat A Y, Said M M, Khalil S A. Aloin: A natural antitumor anthraquinone glycoside with iron chelating and non-atherogenic activities[J]. Pharmaceutical Biology, 2015, 53 (1):138-146.

[6] Vanajothi R, Srinivasan P. An anthraquinone derivative from Luffa acutangula induces apoptosis in human lung cancer cell line NCI-H460 through p53-dependent pathway[J]. Journal of Receptors and Signal Transduction, 2016, 36 (3):292-302.

[7] Machatova Z, Barbierikova Z, Poliak P, et al. Study of natural anthraquinone colorants by EPR and UV/vis spectroscopy[J]. Dyes and Pigments, 2016, 132:79-93.

[8] Zhan Y, Li D, Wei H, et al. Emodin on hepatic fibrosis in rats[J]. Chinese medical journal, 2000, 113 (7):599-601.

[9] Li W Y, Chan R Y K, Yu P H F, et al. Emodin induces cytotoxic effect in human breast carcinoma MCF-7 cell through modulating the expression of apoptosis-related genes[J]. Pharmaceutical Biology, 2013, 51 (9):1175-1181.

[10] Sharma R, Tiku A B. Emodin, an anthraquinone derivative, protects against gamma radiation-induced toxicity by inhibiting DNA damage and oxidative stress[J]. International Journal of Radiation Biology, 2014, 90 (4):275-283.

[11] Wang Q J, Cai X B, Liu M H, et al. Apoptosis induced by emodin is associated with alterations of intracellular acidification and reactive oxygen species in EC-109 cells[J]. Biochemistry and Cell Biology-Biochimie Et Biologie Cellulaire, 2010, 88 (4):767-774.

[12] Astudillo P D, Valencia D P, González-Fuentes M A, et al. Electrochemical and chemical formation of a low-barrier proton transfer complex between the quinone dianion and hydroquinone[J]. Electrochimica Acta, 2012, 81:197-204.

[13] Clare L A, Rojas-Sligh L E, Maciejewski S M, et al. The Effect of H-Bonding and Proton Transfer on the Voltammetry of 2, 3, 5, 6-Tetramethyl-p-phenylenediamine in Acetonitrile. An Unexpectedly Complex Mechanism for a Simple Redox Couple[J]. The Journal of Physical Chemistry C, 2010, 114 (19):8938-8949.

[14] Jin B, Huang J, Zhao A, et al. Direct evidence of hydrogen-bonding and/or protonation effect on p-benzoquinone electrochemical reduction by in situ IR spectroelectrochemical study[J]. Journal of Electroanalytical Chemistry, 2010, 650 (1):116-126.

[15] Kim Y O, Jung Y M, Kim S B, et al. Two-dimensional correlation analysis of spectroelectrochemical data for p-benzoquinone reduction in acetonitrile[J]. Analytical chemistry, 2004, 76 (17):5236-5240.

[16] March G, Reisberg S, Piro B, et al. Electrochemical kinetic analysis of a 1, 4-hydroxynaphthoquinone self-assembled monolayer[J]. Journal of Electroanalytical Chemistry, 2008, 622 (1):37-43.

[17] Quan M, Sanchez D, Wasylkiw M F, et al. Voltammetry of quinones in unbuffered aqueous solution: reassessing the roles of proton transfer and hydrogen bonding in the aqueous electrochemistry of quinones[J]. Journal of the American Chemical Society, 2007, 129 (42):12847-12856.

[18] Gendell J, Miller Jr W R, Fraenkel G K. Electron spin resonance studies of hydroxysemiquinone radicals. Hydrogen-deuterium isotope effects in intramolecular hydrogen bonds[J]. Journal of the American Chemical Society, 1969, 91 (16):4369-4380.

[19] Aguilar-Martínez M, Bautista-Martinez J, Macias-Ruvalcaba N, et al. Molecular structure of substituted phenylamine α-OMe-and α-OH-p-benzoquinone derivatives. Synthesis and correlation of spectroscopic, electrochemical, and theoretical parameters[J]. The Journal of organic chemistry, 2001, 66 (25):8349-8363.

[20] Frontana C, Frontana-Uribe B A, González I. Electrochemical and ESR study on the transformation processes of α-hydroxy-quinones[J]. Journal of Electroanalytical Chemistry, 2004, 573 (2):307-314.

[21] Frontana C, González I. Effects of the molecular structure on the electrochemical properties of naturally occurring α-hydroxyquinones. An electrochemical and ESR study[J]. Journal of Electroanalytical Chemistry, 2007, 603 (2):155-165.

[22] Astudillo Sánchez P D, Evans D H. Reversible dimerization of the anion radicals of some dicyanonaphthalenes[J]. Journal of Electroanalytical Chemistry, 2011, 660 (1):91-96.

[23] Nepomnyashchii A B, Bro?ring M, Ahrens J, et al. Chemical and Electrochemical Dimerization of BODIPY Compounds: Electrogenerated Chemiluminescent Detection of Dimer Formation[J]. Journal of the American Chemical Society, 2011, 133 (48):19498-19504.

[24] Teply? F, C?i?z?kova? M, Slavi?c?ek P, et al. Electron Transfer Triggers Fast Dimer/Monomer Switching of Pyridinium and Quinolinium Cations[J]. The Journal of Physical Chemistry C, 2012, 116 (5):3779-3786.

[25] Maci?as-Ruvalcaba N A, Evans D H. Association Reactions of the Anion Radicals of Some Hydroxyquinones: Evidence for Formation of π-and σ-Dimers As Well As a Neutralˆ’ Anion Radical Complex[J]. The Journal of Physical Chemistry C, 2010, 114 (2):1285-1292.

[26] Cheng W X, Jin B K, Huang P, et al. Investigation on the π-Dimer/σ-Dimer of 1,8-Dihydroxy-9,10-anthracenedione in the Process of Electrochemical Reduction by Using IR Spectroelectrochemical Cyclic Voltabsorptometry and Derivative Cyclic Voltabsorptometry[J]. The Journal of Physical Chemistry C, 2013, 117 (8):3940-3948.

[27] Ossowski T, Pipka P, Liwo A, et al. Electrochemical and UV-spectrophotometric study of oxygen and superoxide anion radical interaction with anthraquinone derivatives and their radical anions[J]. Electrochimica acta, 2000, 45 (21):3581-3587.

[28] Wang X, Jin B, Lin X. In-situ FTIR spectroelectrochemical study of dopamine at a glassy carbon electrode in a neutral solution[J]. Analytical sciences, 2002, 18 (8):931-933.

[29] Jin B K, Li L, Huang J L, et al. IR spectroelectrochemical cyclic voltabsorptometry and derivative cyclic voltabsorptometry[J]. Anal Chem, 2009, 81 (11):4476-4481.

[30] Astuti Y, Topoglidis E, Briscoe P B, et al. Proton-coupled electron transfer of flavodoxin immobilized on nanostructured tin dioxide electrodes: Thermodynamics versus kinetics control of protein redox function[J]. Journal of the American Chemical Society, 2004, 126 (25):8001-8009.

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.