| Reference | [1]. Anal Bioanal Chem. 2021 Mar;413(7):1871-1882. doi: 10.1007/s00216-021-03155-4. Epub 2021 Jan 19.<br />
Novel synthesized attapulgite nanoparticles-based hydrophobic monolithic column for in-tube solid-phase microextraction of thiosildenafil, pseudovardenafil, and norneosildenafil in functional foods.<br />
Dong L(1), Chen Y(2), Chen S(2), Hou C(3), Wang S(1), Xuan R(4), Fang K(2), Wang T(5), Zhang L(3), Zhang Y(3).<br />
Author information: (1)College of Chemical Engineering, Ningbo University of Technology, Ningbo, 315016, Zhejiang, China. (2)Ningbo Academy of Inspection and Quarantine, Ningbo, 315012, Zhejiang, China. (3)Key Laboratory of Separation Science for Analytical Chemistry, National Chromatographic Research and Analysis Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, Liaoning, China. (4)The Affiliated Hospital of Medical School of Ningbo University, Ningbo, 315020, Zhejiang, China. (5)College of Chemical Engineering, Ningbo University of Technology, Ningbo, 315016, Zhejiang, China. [email protected].<br />
In this study, a novel method which involved in-tube solid-phase microextraction (SPME) using an attapulgite (ATP) nanoparticles-based hydrophobic monolithic column was successfully developed. It was coupled with high-performance liquid chromatography-ultraviolet detection for the determination of three phosphodiesterase-5 (PDE-5) inhibitors, including thiosildenafil, pseudovardenafil, and norneosildenafil, in functional foods. The monolithic column was prepared by one-step polymerization, using 3-trimethoxysilylpropyl methacrylate-modified ATP nanoparticles and 1-butyl-3-vinylimidazolium bromide (VBIMBr) as the functional monomers, and ethylene glycol dimethacrylate (EDMA) as the cross-linker. The obtained poly(ATP-VBIMBr-EDMA) monolith was characterized by scanning electron microscopy equipped with energy-dispersive analysis of X-ray, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. The adsorption capacity, up to 2.00 μg/cm calculated by the Langmuir isotherm model, was about six times that of the poly(VBIMBr-EDMA) monolith. Crucial factors affecting the extraction efficiency, including sample solvent, elution solvent, flow rates of sampling loading and elution, sample loading volume, and elution volume, were investigated in details. Under the optimal in-tube SPME conditions, the proposed method showed good reproducibility with run-to-run, column-to-column, and batch-to-batch relative standard deviations less than 7.2%, and low limits of detection of 0.5-0.9 ng/mL in real samples. Thiosildenafil was detected in four types of functional foods with the contents of 1.30-4.78 μg/g. This newly proposed in-tube SPME method based on poly(ATP-VBIMBr-EDMA) monolith may provide a simple, efficient, and promising alternative to daily monitoring of PDE-5 inhibitors in functional foods.<br />
DOI: 10.1007/s00216-021-03155-4 PMID: 33469710 [Indexed for MEDLINE]<br />
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[2]. J Mass Spectrom. 2014 Dec;49(12):1279-89. doi: 10.1002/jms.3461.<br />
Structure elucidation of phototransformation products of unapproved analogs of the erectile dysfunction drug sildenafil in artificial freshwater with UPLC-Q Exactive-MS.<br />
Aceña J(1), Pérez S, Gardinali P, Abad JL, Eichhorn P, Heuett N, Barceló D.<br />
Author information: (1)Water and Soil Quality Research Group, IDAEA-CSIC, c/Jordi Girona 18-26, 08034, Barcelona, Spain.<br />
In this study, four unapproved analogues of Sildenafil (SDF) were photodegraded under synthetic sunlight in artificial freshwater. Homosildenafil (H-SDF), hydroxyhomo-sildenafil (HH-SDF), norneosildenafil (NR-SDF) and thiosildenafil (T-SDF) were selected because they are frequently detected as adulterants in natural herbal products. Using UPLC-Orbitrap (Q Exactive)-MS, six photoproducts common to H-SDF, HH-SDF and T-SDF and nine unique transformation products of different molecular weights were identified based on their high-resolution (+)ESI product ion spectra. Mass spectral analysis of deuterated H-SDF, labeled on the N-ethyl group, allowed to gain mechanistic insight into the fragmentation pathway of the substituted piperazine ring and to support the postulated photoproduct structures. The mass spectral fragmentation confirmed the stepwise destruction of the piperazine ring eventually producing a sulfonic acid derivative (C17 H20 N4 O5 S: 392.1151 Da). In contrast, the photodegradation of NR-SDF, which lacks a piperazine ring in its structure, formed only two prominent photoproducts originating from N,N-dealkylation of the sulfonamide followed by hydrolysis. The current work constitutes the first study on the photodegradation of analogs of erectile dysfunction drugs and the first detection of two transformation products (m/z 449 and 489) in environmental samples.<br />
DOI: 10.1002/jms.3461 PMID: 25476946 [Indexed for MEDLINE]
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