| Reference | [1]. J Pharm Biomed Anal. 2018 Nov 30;161:61-65. doi: 10.1016/j.jpba.2018.08.031. Epub 2018 Aug 18.<br />
Characterization of a new illicit phosphodiesterase-type-5 inhibitor identified in the softgel shell of a dietary supplement.<br />
Doi T(1), Takahashi K(2), Yamazaki M(2), Asada A(3), Takeda A(3), Kiyota K(3), Tagami T(3), Sawabe Y(3), Yamano T(3).<br />
Author information: (1)Department of Hygienic Chemistry, Osaka Institute of Public Health, 1-3-69 Nakamichi, Higashinari-ku, Osaka 537-0025, Japan. Electronic address: [email protected]. (2)Chiba Prefectural Institute of Public Health, 666-2 Nitona-cho, Chuo-ku, Chiba, Chiba 260-8715, Japan. (3)Department of Hygienic Chemistry, Osaka Institute of Public Health, 1-3-69 Nakamichi, Higashinari-ku, Osaka 537-0025, Japan.<br />
A new sildenafil analog has been identified in the softgel shell of a dietary supplement. The compound was investigated by UV spectroscopy and high-resolution MS analysis, leading to the proposed structure 1-methyl-5-{5-[2-(4-methylpiperazin-1-yl)acetyl]-2-propoxyphenyl}-3-propyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one. A synthetic reference compound with the proposed structure was prepared, and the two sets of analytical data were compared, confirming the structure of the new compound. The compound was named propoxyphenyl noracetildenafil from its structure and similarity with the known compound.<br />
DOI: 10.1016/j.jpba.2018.08.031 PMID: 30145450 [Indexed for MEDLINE]<br />
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[2]. J Chromatogr A. 2014 May 30;1344:91-8. doi: 10.1016/j.chroma.2013.12.030. Epub 2013 Dec 17.<br />
Application of a high resolution benchtop quadrupole-Orbitrap mass spectrometry for the rapid screening, confirmation and quantification of illegal adulterated phosphodiesterase-5 inhibitors in herbal medicines and dietary supplements.<br />
Shi F(1), Guo C(2), Gong L(1), Li J(1), Dong P(1), Zhang J(3), Cui P(4), Jiang S(1), Zhao Y(1), Zeng S(5).<br />
Author information: (1)Shandong Institute for Food and Drug Control, Jinan, Shandong 250101, PR China. (2)Shandong Institute for Food and Drug Control, Jinan, Shandong 250101, PR China. Electronic address: [email protected]. (3)Cancer Center, Linyi's People Hospital, Linyi 276000, PR China. Electronic address: [email protected]. (4)Service team, Thermo Fisher Scientific, Beijing 100007, PR China. (5)Lab of Pharmaceutical Analysis and Drug Metabolism, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou, Zhejiang 310058, PR China.<br />
In this study, the applicability of high resolution quadrupole-Orbitrap (Q-Orbitrap) mass spectrometry for the simultaneous qualitative and quantitative analysis of illegal adulterated phosphodiesterase-5 inhibitors (PDE-5 inhibitors) in herbal medicines and dietary supplements was investigated. The mass spectrometer was operated in full MS scan/dd-MS(2) (data-dependent MS(2)) mode. The use of 70,000 FWHM mass resolution and narrow mass windows (5 ppm) could effectively improve the selectivity of the method, increasing the signal-to-noise ratio for the analytes. The response showed good linear relationship with the analytes' concentrations over wide ranges (e.g., 0.05-10 μg/g for sildenafil) with all the coefficient of determinations (r(2)) >0.9996. The detection limits (LODs) were in the range of 1.0-5.0 ng/g for different analytes. The recoveries ranged from 85.4% to 96.7%. The intra- and inter-day accuracies were in the range of -6.6 to 10.1%, while the intra- and inter-day precision ranged from 0.0039% to 13.2%. Among 68 batches of herbal medicines and 20 batches of dietary supplements (including 83 capsules, 3 pellets and 2 liquid) samples, sildenafil was detected in 8 dietary supplements, while noracetildenafil was detected in only one dietary supplement. The novel Q-Orbitrap mass spectrometry has been proved to be a very promising and powerful tool for routine screening of illegal adulterate in herbal medicines and dietary supplements, ensuring food safety and public health.<br />
DOI: 10.1016/j.chroma.2013.12.030 PMID: 24377735 [Indexed for MEDLINE]<br />
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[3]. Se Pu. 2015 Aug;33(8):897-901. doi: 10.3724/sp.j.1123.2015.03020.<br />
[Rapid screening and confirmation of illegally added anti- impotence preparations in health care products by high performance liquid chromatography-high resolution mass spectrometry].<br />
[Article in Chinese]<br />
Hu T, Qu X, Kang M, Song Q, Yang L, Zhao Y, Zhang D.<br />
A method was established for rapid screening and quantifying 11 illegally added anti-impotence preparations (yohimbine, acetildenafil, nor-acetildenafil, homosildenafil, hydroxy-homosildenafil, sildenafil, vardenafil, thioaildenafil, tadalafil, pseudovardenafil, dapoxetine) in health care products by high performance liquid chromatography-high resolution mass spectrometry. The samples were extracted with methanol and analyzed by positive mode in the MS detection. The results showed that the limits of detection were 25.0 ng/mLexcept for nor-acetildenafil (5.0 ng/mL), the linear ranges were 5.0-200.0 ng/mL except for nor-acetildenafil (25.0-500.0 ng/mL) with the correlation coefficients not less than 0.999 0. The recoveries were in the range of 82.0%-105.9% with the relative standard deviations of 4.7%-16.5%. This method is accurate, simple and rapid, and can be used in rapid screening and quantitative analysis of the 11 illegally added anti-impotence in health care products.<br />
DOI: 10.3724/sp.j.1123.2015.03020 PMID: 26749869 [Indexed for MEDLINE]<br />
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[4]. J Pharm Biomed Anal. 2007 Aug 15;44(4):887-93. doi: 10.1016/j.jpba.2007.04.011. Epub 2007 Apr 18.<br />
Use of liquid chromatography-mass spectrometry and a chemical cleavage reaction for the structure elucidation of a new sildenafil analogue detected as an adulterant in an herbal dietary supplement.<br />
Reepmeyer JC(1), Woodruff JT.<br />
Author information: (1)U.S. Food and Drug Administration, Division of Pharmaceutical Analysis, St. Louis, MO 63101, USA. [email protected]<br />
An herbal dietary supplement, marketed as a natural product for the enhancement of sexual function, was analyzed by HPLC with photodiode array and mass spectral detection and found to contain a compound related to the synthetic phosphodiesterase-5 (PDE-5) inhibitors. Based on UV spectra, mass spectra and direct infusion MS(n), the structure of the compound was tentatively identified as a sildenafil analogue in which the sulfonyl group had been replaced with an acetyl group. This new analogue is similar to acetildenafil, a previously reported sildenafil analogue, but differs in that it contains an N-methyl group where acetildenafil contains an N-ethyl group. The structure of the unknown was unequivocally established by chemical cleavage of the phenacylamine group of the molecule to generate N-methylpiperazine; other cleavage products matched those generated from acetildenafil. Since the new compound has one less CH(2) group than acetildenafil, it was named nor-acetildenafil.<br />
DOI: 10.1016/j.jpba.2007.04.011 PMID: 17532168 [Indexed for MEDLINE]
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