Abstract
Di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium [DPPH] is widely used as a standard for measuring the number of free radicals. Here, we evaluated the number of free radicals of “DPPH” reagents from three manufacturers by effective magnetic moment method. Interestingly, the reagents from different manufacturers had varying temperature dependencies for both magnetic moment and g-value at low temperatures. As a result, the maximum relative difference among the three reagents on the number of free radicals per unit mass was 20%. Carbon hydrogen nitrogen (CHN) analyses, highresolution EPR measurements, FT-IR measurement, and NMR measurement confirmed that a major component of only one among the three reagents was “pure” DPPH. The evaluated purity based on free radical content was 0.998 kg kg–1 with expanded uncertainty of 0.036 kg kg–1. The other two reagents were found to be contaminated by several % of benzene in the DPPH crystal structure.
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D. A. Skoog, D. M. West, F. J. Holler, and S. R. Crouch, “Analytical Chemistry: An Introduction”, 7th ed., 2000, Saunders College Publishing, A Division of Harcourt College Publishers, Orlando, FL.
M. J. T. Milton and T. J. Quinn, Metrologia, 2001, 38, 289.
N. Matsumoto and K. Kato, Metrologia, 2012, 49, 530.
N. Matsumoto and T. Shimosaka, Accred. Quality Assur., 2015, 20, 115.
N. Matsumoto and T. Shimosaka, J. Appl. Phys., 2015, 117, 17E114.
N. Matsumoto and T. Shimosaka, Anal. Sci., 2017, 33, 1059.
N. Matsumoto, Bunseki, 2016, 63.
T. Kikuchi, K. Kikugawa, and T. Kato, Chem. Pharm. Bull., 1980, 28, 2089.
W. Brand-Williams, M. E. Cuvelier, and C. Berset, Food Sci. Technol LWT, 1995, 28, 25.
D. Sanna, G. Delogu, M. Mulas, M. Schirra, and A. Fadda, Food Anal. Methods, 2012, 5, 759.
E. V. Piletska, S. S. Piletsky, M. J. Whitcombe, I. Chianella, and S. A. Piletsky, Anal. Chem., 2012, 84, 2038.
P. Nagaraja, N. Aradhana, A. Suma, A. Shivakumar, and N. A. Chamaraja, Anal. Sci., 2014, 30, 251.
T. Shimamura, Y. Sumikura, T. Yamazaki, A. Tada, T. Kashiwagi, H. Ishikawa, T. Matsui, N. Sugimoto, H. Akiyama, and H. Ukeda, Anal. Sci., 2014, 30, 717.
I. Nakanishi, K. Ohkubo, K. Imai, M. Kamibayashi, Y. Yoshihashi, K. Matsumoto, K. Fukuhara, K. Terada, S. Itoh, T. Ozawa, and S. Fukuzumi, Chem. Commun., 2015, 57, 8311.
D. Li, J. Jiang, D. Han, X. Yu, K. Wang, S. Zang, D. Lu, A. Yu, and Z. Zhang, Anal. Chem., 2016, 88, 3885.
L. Wang, W. Ma, S. Gan, D. Han, Q. Zhang, and L. Niu, Anal. Chem., 2014, 86, 10171.
D. B. Hunsaker, Jr. and G. H. Schenk, Talanta, 1983, 30, 475.
The Society of Electron Spin Science and Technology, “Introduction to Electron Spin Science and Technology”, 2010, Chap. 5, Sangyo-tosho Co. Ltd., Tokyo.
K. Komaguchi, T. Maruoka, H. Nakano, I. Imae, Y. Ooyama, and Y. Harima, J. Phys. Chem. C, 2010, 114, 1240.
K. Nakagawa, S. Minakawa, D. Sawamura, and H. Hara, Anal. Sci., 2017, 33, 1357.
J. Krzystek, A. Sienkiewicz, L. Pardi, and L. C. Brunei, J. Mag. Reson., 1997, 125, 207.
B. Cage, A. Weekiey, L. C. Brunei, and N. S. Daiai, Anal. Chem., 1999, 71, 1951.
R. Miyamoto, M. Iwaki, H. Mino, J. Harada, S. Itoh, and H. Oh-oka, Biochemistry, 2006, 45, 6306.
B. Rakvin, D. Žilić, N. S. Dalai, J. M. North, P. Cevc, D. Arčon, and K. Zadro, Spectrochim. Acta, Part A, 2004, 60, 1241.
H. Takahashi, T. Okamoto, E. Ohmichi, and H. Ohta, Appl. Phys. Express, 2016, 9, 126701.
M. Ikeya, Anal. Sci., 1989, 5, 5.
M. Furusawa and M. Ikeya, Anal. Sci., 1988, 4, 649.
J. P. Campbell, J. T. Ryan, P. R. Shrestha, Z. Liu, C. Vaz, J-H. Kim, V. Georgiou, and K. P. Cheung, Anal. Chem., 2015, 87, 4910.
H. Hirata, T. Kuyama, M. Ono, and Y. Shimoyama, J. Mag. Reson., 2003, 164, 233.
T. Suzuki, J. Mag. Reson., 2015, 259, 95.
ISO Guide 35-2006, “Reference Materials—General and Statistical Principles for Certification”, 3rd ed., 2006, International Organization for Standardization, Switzerland, 31.
R. T. Weidner and C. A. Whitmer, Phys. Rev., 1953, 91, 1279.
D. E. Williams, J. Am. Chem. Soc., 1967, 89, 4280.
N. Ohigashi and H. Inokuchi, Bull. Chem. Soc. Jpn., 1969, 42, 1212.
T. Fujito, T. Enoki, H. Ohya-Nishiguchi, and Y. Deguchi, Chem. Lett., 1972, 557.
B. N. Misra and S. K. Gupta, Bull. Chem. Soc. Jpn., 1973, 46, 3067.
R. Verlinden, P. Grobet, and L. Van Gerven, Chem. Phys. Lett., 1974, 27, 535.
T. Yoshioka, H. Ohya-Nishiguchi, and Y. Deguchi, Bull. Chem. Soc. Jpn., 1974, 47, 430.
W. Duffy, D. L. Strandburg, and J. F. Deck, J. Chem. Phys., 1978, 68, 2097.
T. Fujito, Bull. Chem. Soc. Jpn., 1981, 54, 3110.
N. D. Yodanov and A. Christova, Appl. Magn. Reson., 1993, 6, 341.
N. D. Yodanov, Appl. Magn. Reson., 1996, 70, 339.
D. Žilić, D. Pajić, M. Jurić, K. Molćanov, B. Rakvin, P. Planinić, and K. Zadro, J. Magn. Reson., 2010, 207, 34.
N. Itoh, T. Yamazaki, A. Sato, M. Numata, and A. Takatsu, Anal. Sci., 2014, 30, 471.
N. Itoh, A. Sato, T. Yamazaki, M. Numata, and A. Takatsu, Anal. Sci., 2013, 29, 1209.
H. Fisher, SpringerMaterials, 2.2.2 Nitrogen radicals, Landolt-Börnstein—Group II Molecules and Radicals 1 (Magnetic Properties of Free Radicals), ed. K.-H. Hellwege and A. M. Hellwege, 1965, Chapter DOI:10.1007/10201179_9, Springer-Verlag, Berlin Heidelberg.
P. H. Rieger, “Electron Spin Resonance: Analysis and Interpretation”, 2007, RSC Publishing, Cambridge, 102.
C. Corvaja, “Electron Paramagnetic Resonance: A Practitioner’s Toolkit”, ed. M. Burustolon and E. Giamello, 2009, John Wiley & Sons, Inc., NJ.
M. Kohno, “Electron Spin Resonance (in Japanese)”, 2003, Chap. 3, Ohmsha.
SDBSWeb: http://sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, Jan 2018).
R. M. Silverstein, G. C. Bassler, and T. C. Morrill, “Spectroscopic Identification of Organic Compounds”, 5th ed., 1991, Chap. 3, John Wiley & Sons, Inc., New York.
F. Gerson and W. Huber, “Electron Spin Resonance Spectroscopy for Organic Radicals”, 2003, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 296.
NIST Chemistry WebBook: Compilation prepared by the National Institute of Standard and Technology, http://webbook.nist.gov/chemistry/.
Acknowledgments
A major part of this work was conducted at the Institute for Molecular Science, National Institutes of Natural Sciences, supported by the Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. Part of the SQUID measurements was conducted at the AIST Nano- Processing Facility, supported by the Nanotechnology Platform Program of the same ministry. The authors would like to thank Dr. K. Yamazaki (AIST) for the NMR measurements. An Excel macro program formulated by Dr. T. Shimosaka (AIST) was used for data fitting of magnetic moment via least-squared method. This work was supported by JSPS KAKENHI Grant Number JP17K05918.
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Matsumoto, N.O., Itoh, N. Measuring Number of Free Radicals and Evaluating the Purity of Di(phenyl)-(2,4,6-trinitrophenyl)iininoazaniuin [DPPH] Reagents by Effective Magnetic Moment Method. ANAL. SCI. 34, 965–971 (2018). https://doi.org/10.2116/analsci.18P120
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DOI: https://doi.org/10.2116/analsci.18P120