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Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry.

Huang XY, Guo XL, Luo HL, Fang XW, Zhu TG, Zhang XL, Chen HW, Luo LP - Int J Anal Chem (2015)

Bottom Line: Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively.Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated.Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis.

View Article: PubMed Central - PubMed

Affiliation: School of Life Sciences, Nanchang University, Nanchang, Jiangxi 330031, China.

ABSTRACT
Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis.

No MeSH data available.


The MS2 spectra of propolis. (a) MS spectrum of propolis sample 1 (HLJ) and 253, 255, and 301 m/z are indicated by arrows. (b), (d), and (f), MS2 spectra of reference standards of quercetin (b), chrysin (d), and pinocembrin (f). (c), (e), and (g), MS2 spectra of 253 m/z (c), 255 (e), and 301 (g) in MS spectrum of propolis sample 1 (HLJ).
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fig3: The MS2 spectra of propolis. (a) MS spectrum of propolis sample 1 (HLJ) and 253, 255, and 301 m/z are indicated by arrows. (b), (d), and (f), MS2 spectra of reference standards of quercetin (b), chrysin (d), and pinocembrin (f). (c), (e), and (g), MS2 spectra of 253 m/z (c), 255 (e), and 301 (g) in MS spectrum of propolis sample 1 (HLJ).

Mentions: Most Chinese propolis belongs to the poplar type and is rich in health promoting phenolic compounds [28, 34, 35]. All propolis samples in the present study were analyzed by HPLC. Previous study indicated that 9 chemicals, including chrysin, pinocembrin, and quercetin, were common in Chinese propolis samples, except in the one (named YN-2 in this paper) from Xishuangbanna, a tropical region in Yunnan province [4, 12]. Therefore, chrysin, pinocembrin, and quercetin were detected by reference standards for confirmation [12]. In the SDAPCI mass spectra of 200 to 350 m/z for the propolis samples, possible signals corresponding to the afore-mentioned chemicals can be noted (Figure 3(a)). Therefore, we undertook further experiments to characterize these signals. Using SDAPCI-MS analysis of the standard solutions, the negative ion ([M–H]−) of chrysin (253 m/z) generated major fragment ions at 235, 225, 209, and 191 m/z (Figure 3(b)), the negative ion ([M–H]−) of pinocembrin (255 m/z) generated major fragment ions at 237, 221, 213, 211, and 193 m/z (Figure 3(d)), and the negative ion ([M–H]−) of quercetin (301 m/z) generated major fragment ions at 285, 283, and 217 m/z (Figure 3(f)). For 253, 255, and 301 m/z in the SDAPCI-MS fingerprint of crude propolis, similar MS2 spectra were obtained to those for the reference standards of chrysin, pinocembrin, and quercetin. Similar results were observed for all propolis samples except YN-2, and the spectra for sample HLJ were shown as an example in Figures 3(c), 3(e), and 3(g). Thus, it was confirmed that chrysin, pinocembrin, and quercetin in crude propolis can be detected by SDAPCI-MS without sample pretreatment.


Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry.

Huang XY, Guo XL, Luo HL, Fang XW, Zhu TG, Zhang XL, Chen HW, Luo LP - Int J Anal Chem (2015)

The MS2 spectra of propolis. (a) MS spectrum of propolis sample 1 (HLJ) and 253, 255, and 301 m/z are indicated by arrows. (b), (d), and (f), MS2 spectra of reference standards of quercetin (b), chrysin (d), and pinocembrin (f). (c), (e), and (g), MS2 spectra of 253 m/z (c), 255 (e), and 301 (g) in MS spectrum of propolis sample 1 (HLJ).
© Copyright Policy - open-access
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4539062&req=5

fig3: The MS2 spectra of propolis. (a) MS spectrum of propolis sample 1 (HLJ) and 253, 255, and 301 m/z are indicated by arrows. (b), (d), and (f), MS2 spectra of reference standards of quercetin (b), chrysin (d), and pinocembrin (f). (c), (e), and (g), MS2 spectra of 253 m/z (c), 255 (e), and 301 (g) in MS spectrum of propolis sample 1 (HLJ).
Mentions: Most Chinese propolis belongs to the poplar type and is rich in health promoting phenolic compounds [28, 34, 35]. All propolis samples in the present study were analyzed by HPLC. Previous study indicated that 9 chemicals, including chrysin, pinocembrin, and quercetin, were common in Chinese propolis samples, except in the one (named YN-2 in this paper) from Xishuangbanna, a tropical region in Yunnan province [4, 12]. Therefore, chrysin, pinocembrin, and quercetin were detected by reference standards for confirmation [12]. In the SDAPCI mass spectra of 200 to 350 m/z for the propolis samples, possible signals corresponding to the afore-mentioned chemicals can be noted (Figure 3(a)). Therefore, we undertook further experiments to characterize these signals. Using SDAPCI-MS analysis of the standard solutions, the negative ion ([M–H]−) of chrysin (253 m/z) generated major fragment ions at 235, 225, 209, and 191 m/z (Figure 3(b)), the negative ion ([M–H]−) of pinocembrin (255 m/z) generated major fragment ions at 237, 221, 213, 211, and 193 m/z (Figure 3(d)), and the negative ion ([M–H]−) of quercetin (301 m/z) generated major fragment ions at 285, 283, and 217 m/z (Figure 3(f)). For 253, 255, and 301 m/z in the SDAPCI-MS fingerprint of crude propolis, similar MS2 spectra were obtained to those for the reference standards of chrysin, pinocembrin, and quercetin. Similar results were observed for all propolis samples except YN-2, and the spectra for sample HLJ were shown as an example in Figures 3(c), 3(e), and 3(g). Thus, it was confirmed that chrysin, pinocembrin, and quercetin in crude propolis can be detected by SDAPCI-MS without sample pretreatment.

Bottom Line: Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively.Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated.Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis.

View Article: PubMed Central - PubMed

Affiliation: School of Life Sciences, Nanchang University, Nanchang, Jiangxi 330031, China.

ABSTRACT
Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis.

No MeSH data available.