Direct Analysis of Navel Orange Using Internal Extractive Electrospray Ionization Mass Spectrometry†

doi:10.7503/cjcu20150233

Abstract

Abstract:

Internal extractive electrospary ionization mass spectrometry(iEESI-MS) was applied on the assessment of navel orange quality without any sample pretreatment. Both endocarp tissues(72 samples) and flesh tissues(72 samples) of navel oranges from three habitats were interrogated directly by iEESI-MS at mass range of m/z 50—2000. A fused silicon capillary was inserted into the navel orange tissue, allowing a distance of 2 mm between the fused silicon capillary tip and the sample apex. The apex of the sample was pointed to the mass spectrometer ion inlet intentionally with a distance of 4—5 mm. Extraction solvent biased with a high voltage(4.5 kV) was injected through the fused silicon capillary into the navel orange tissue at a flow rate of 2 μL/min, producing charged fine droplets containing chemicals toward the adjacent mass spectrometer inlet. Chemical constituents such as sugars, amino acids, vitamin and alkaloids were simultaneously extracted from the navel orange tissue, and identified through collision-induced dissociation(CID) experiment. Furthermore, mass spectral fingerprints were processed by principal component analysis(PCA) to visualize the quality differences. Our experimental results indicated that iEESI-MS can directly characterize the quality differences of navel oranges by molecular analysis. The merits of iEESI-MS include simplicity, good specificity, high throughput and minimum sample pretreatment.

Key words: Internal extractive electrospary ionization mass spectrometry, Navel orange, Quality assessment, Direct analysis

TrendMD:

LU Haiyan, ZHANG Hua, ZHOU Peng, YANG Meiling, ZHONG Tao, YAO Guocan, CHEN Huanwen. Direct Analysis of Navel Orange Using Internal Extractive Electrospray Ionization Mass Spectrometry^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 1912.

Figures/Tables 7

Fig.1 Schematic diagram of iEESI-MS

Fig.2 iEESI-MS spectra of orange flesh from different habitats(A) Guoxi; (B) Anxi; (C) Yongxing.

Fig.3 MS2 spectra of choline(A), proline(B), stachydrine(C) and sucrose(D) from orange flesh

Fig.4 PCA score plots(A) and PCA loading plots(B) of iEESI-MS data of orange flesh from different habitats a. Guoxi; b. Anxi; c. Yongxing.

Fig.5 iEESI-MS spectra of orange endocarp from different habitats(A) Guoxi; (B) Anxi; (C) Yongxing.

Table 1 Summary of the dominant chemicals in navel orange from different habitats detected by iEESI-MS*

Habitat	Sampling position	Dominant mass spectra peaks
		m/z 104	m/z 116	m/z 144	m/z 168	m/z 175	m/z 219	m/z 381	m/z 403
		Choline	Proline	Stachydrine	Synephrine	Arginine	Glucose/ fructose	Sucrose	Nobiletin
		C₅H₁₄NO⁺	C₅H₁₀N $O 2 +$	C₇H₁₀N $O 2 +$	C₉H₁₄N $O 2 +$	C₆H₁₅N₄ $O 2 +$	C₆H₁₂O₆K⁺	C₁₂H₂₂O₆K⁺	C₂₁H₂₃ $O 8 +$
Guoxi	Flesh	+	++	++++	+	+	++++	+++	+
	Endocarp	+	++	+++	++++	+	++++	++	+
Anxi	Flesh	+	++	++++	+	+	+++	+++	+
	Endocarp	+	++	+++	++++	+	++++	+++	+
Yongxing	Flesh	+	+++	+++	+	+	++++	+++	+
	Endocarp	+	+	++	+++	+	++++	+	+

Table 1 Summary of the dominant chemicals in navel orange from different habitats detected by iEESI-MS*

Habitat	Sampling position	Dominant mass spectra peaks
		m/z 104	m/z 116	m/z 144	m/z 168	m/z 175	m/z 219	m/z 381	m/z 403
		Choline	Proline	Stachydrine	Synephrine	Arginine	Glucose/ fructose	Sucrose	Nobiletin
		C₅H₁₄NO⁺	C₅H₁₀N $O 2 +$	C₇H₁₀N $O 2 +$	C₉H₁₄N $O 2 +$	C₆H₁₅N₄ $O 2 +$	C₆H₁₂O₆K⁺	C₁₂H₂₂O₆K⁺	C₂₁H₂₃ $O 8 +$
Guoxi	Flesh	+	++	++++	+	+	++++	+++	+
	Endocarp	+	++	+++	++++	+	++++	++	+
Anxi	Flesh	+	++	++++	+	+	+++	+++	+
	Endocarp	+	++	+++	++++	+	++++	+++	+
Yongxing	Flesh	+	+++	+++	+	+	++++	+++	+
	Endocarp	+	+	++	+++	+	++++	+	+

Fig.6 PCA score plots(A) and PCA loading plots(B) of iEESI-MS data of orange endocarp from different habitats

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