Antioxidant activities and liquid chromatography with electrospray ionization tandem mass spectrometry characterization and quantification of the polyphenolic contents of Rumex nervosus Vahl leaves and stems.

In the present study, four compounds, viz. chlorogenic acid, catechin, orientin, and apigenin-O-acetylglycoside among 18 polyphenol compounds (17 flavonoids and one hydroxycinnamic acid derivative) were characterized for the first time in Rumex nervosus leaves and stems by using liquid chromatography with electrospray ionization tandem mass spectrometry. Method validation in terms of determination coefficient, limits of detection, and quantification were ≥ 0.9979, 0.68-1.61, and 2.27-5.38 mg/L, respectively. Accuracy, expressed as percent recovery for two spiking levels (10 and 50 mg/L), were in the range 78.9-110.6% with the exception of caffeic acid. The relative standard deviations were 1-17%. The total polyphenol content was higher by approximately two times in the leaf (1073 mg/kg fresh sample) than in the stem (519.86 mg/kg fresh sample). The antioxidant effects increased in a dose-dependent manner, and the scavenging activities, investigated by measuring 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) scavenging activity, ferrous ions chelating activity, superoxide anion radical scavenging activity, and ferric reducing antioxidant power activity, were significant (p < 0.05) using low concentrations of the leaf extract. Overall, the present study suggests that different parts of R. nervosus have great potential for producing a range of extracts with potential applications in medicine.

The effects of different night-time temperatures and cultivation durations on the polyphenolic contents of lettuce: Application of principal component analysis.

The present study was conducted to characterize the polyphenolic contents of lettuce leaves grown under different night-time temperatures (4, 12, and 20 °C) and cultivation durations (5, 15, and 20 days) using high performance liquid chromatography-tandem mass spectrometry (LC/MS/MS). The assay method was validated based on specificity, linearity, accuracy, precision, and the performance limit. The total polyphenolic contents were highest (2462.6 mg/kg) after transplantation at a night temperature of 20 °C on day 20 and lowest (1132.7 mg/kg) at the same temperature on day 5. Quantification and principal component analysis showed that the relative contents of quercetin and kaempferol were markedly higher during the early stage of cultivation (day 5) than those of day 15 and 20, and that night-time temperatures of 12 and 20 °C on day 20 were favorable for producing polyphenol-rich lettuce containing caffeic acid. In conclusion, a synergistic effect between high night-time temperatures (12 and 20 °C) and cultivation duration (20 days) produced lettuce rich in polyphenols compared to that at low temperature (4 °C).

Phospholipid profiling of 57 soybean (Glycine max) varieties by high-performance liquid chromatography-tandem mass spectrometry and principal component analysis to classify Korean soybean germplasm.

Phospholipids (PLs) in 57 varieties of soybeans were profiled by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry and principal component analysis (PCA) to discriminate PL-rich soybeans. The PL calibration curves showed linearity with correlation coefficients >0.9964. The recoveries at 5 mg/L spiked level ranged from 72.8 to 86.7% and those at 12.5 mg/L from 78.2 to 85.1%. The repeatability at a 5 mg/L spiked level ranged from 2.5 to 7.0% and those at 12.5 mg/L from 1.2 to 3.9%. The average total PL content in the 57 soybean varieties was about 35.3 mg/kg. The total PL content was the highest in Aodaiz (35, 48.7 ± 1.4 mg/kg) and the lowest in Poongsannamul (56, 16.0 ± 0.7 mg/kg). The PCA showed that RS-78sun (42), Gyeongsang #1 (3) and Aodaiz (35) are the most improved varieties of the investigated 57 varieties from the viewpoint of PL content.

Influences of four different light-emitting diode lights on flowering and polyphenol variations in the leaves of chrysanthemum (Chrysanthemum morifolium).

Light-emitting diodes (LEDs) are an efficient alternative to traditional lamps for plant growth. To investigate the influence of LEDs on flowering and polyphenol biosynthesis in the leaves of chrysanthemum, the plants were grown under supplemental blue, green, red, and white LEDs. Flower budding was formed even after a longer photoperiod than a critical day length of 13.5 h per day under blue light illumination. The weights of leaves and stems were highest under the white light illumination growth condition, whereas the weight of roots appeared to be independent of light quality. Among nine polyphenols characterized by high-performance liquid chromatography-tandem mass spectroscopy, three polyphenols were identified for the first time in chrysanthemum. A quantitation and principal component analysis biplot demonstrated that luteolin-7-O-glucoside (2), luteolin-7-O-glucuronide (3), and quercetagetin-trimethyl ether (8) were the highest polyphenols yielded under green light, and dicaffeoylquinic acid isomer (4), dicaffeoylquinic acid isomer (5), naringenin (7), and apigenin-7-O-glucuronide (6) were greatest under red light. Chlorogenic acid (1) and 1,2,6-trihydroxy-7,8-dimethoxy-3-methylanthraquinone (9) were produced in similar concentrations under both light types. The white and blue light appeared inefficient for polyphenol production. Taken together, our results suggest that the chrysanthemum flowering and polyphenol production are influenced by light quality composition.

Determination of the change of flavonoid components as the defence materials of Citrus unshiu Marc. fruit peel against Penicillium digitatum by liquid chromatography coupled with tandem mass spectrometry.

A healthy fruit peel of Citrus unshiu Marc. and one infected by Penicillium digitatum were analysed for flavonoids via high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) in the positive mode with selected ion monitoring (SIM). Among 16 flavonoid components characterised in C. unshiu Marc., four flavanones and nine flavones were identified for the first time. The identified compounds were quantified by HPLC-UV. To investigate the function of the flavonoids as defence materials, the flavonoid content change of the fruit peel inoculated with P. digitatum was monitored by HPLC. The flavonoid concentration in the infected fruit peel decreased initially after the infection and then gradually increased before finally progressively decreasing.

Simultaneous determination of phoxim and its photo-transformation metabolite residues in eggs using liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

The principal objective of this study was to develop an appropriate, sensitive, and selective method for the simultaneous quantitative determination of phoxim and its photo-transformation product, O,O-diethyl alpha-cyanobenzylideneamino-thiophosphonate (DCTP) in both chicken and quail eggs. Eggs (1 g) were blended with anhydrous magnesium sulfate (1 g) for sample pretreatment and extracted with acetonitrile. The extracts were then further purified with SPE silica gel tubes deactivated with trimethylamine. Residues were analyzed via a reversed phase-liquid chromatography-tandem mass spectrometry (RP-LC-MS/MS) in positive-ion electrospray ionization (ESI) mode. Tebufenozide was utilized as an internal standard for the quantification of phoxim and its metabolite residues. The identification and quantification of analytes were based on ion transitions monitored by multiple reaction monitoring (MRM). LC-MS/MS analysis was performed from 0.02 to 1 mg kg(-1) and correlation coefficients (r(2)) ranging from 0.998 to 0.999 were obtained for both analytes in blank egg extracts. The relative standard deviations (RSDs) of intra- and inter-day variations ranged from 2.1% to 6.7% and from 2.8% to 6.4% for phoxim and DCTP in chicken and quail eggs. At all levels of fortification (0.02, 0.05, and 0.125 mg kg(-1)), the recoveries fell within a range of 81.3% to 93.6% for phoxim and 83.3% to 90.1% for DCTP. The matrix effect was <2%, due to the partial dilution of the sample. Decision limits (CCalpha) and detection capabilities (CCbeta) were in the range of 0.0005-0.0044 and 0.0054-0.0224 mg kg(-1), respectively. The method was evaluated further by analyzing real samples purchased from markets. All chicken and quail egg samples were free from residues of the target compounds.

Residue analysis of multi-class pesticides in watermelon by LC-MS/MS.

As watermelon is farmed primarily by protected and successive cultivation techniques, a number of pesticides are required for the control of pests and diseases. To evaluate the harmful effects of pesticides in watermelon and to guarantee consumers' safety, a rapid screening process for pesticides is required. A LC-MS/MS method was applied for the direct quantitation of 44 pesticide residues in watermelon. A Zorbax XDB-C(18) column was selected for analysis, with a mobile phase consisting of a gradient system of water and 5 mM methanolic ammonium formate. MS/MS experiments were performed in ESI positive ion and multiple reaction monitoring modes. The LOQs were in the range of 1-26 microg/kg, thereby indicating good sensitivity. Most of the recoveries ranged between 70-131% with RSDs < or = 20%. We suggested that the amount of pesticide residues such as pyroquilon (pyn), boscalid (bd), and dimethomorph (di) in amides (AM) and cinosulfuron (ci) in ureas (UR) may have been overestimated for the pesticides owing to increased alpha-error risk, whereas the amounts of pesticide residues, such as imibenconazole (ie) in the triazoles (TR) and fenpyroximate (fee) in the imidazoles (IM), may have been underestimated as the result of increased beta-error risk. The current method allowed for the rapid quantitation and identification of low pesticide levels in the watermelon samples. No pesticide residues were detected in any of the surveyed watermelons obtained from eight local markets in the Republic of Korea. Statistical analysis of the recoveries classified the 44 pesticides into nine groups and three overall categories.

Multiresidue analysis of pesticides with hydrolyzable functionality in cooked vegetables by liquid chromatography tandem mass spectrometry.

It would be preferable for pesticide residues substituted by hydrolyzable functionality to be analyzed after cooking because their structures are apt to degrade during boiling and/or heating. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the quantitative determination of 44 pesticide residues with hydrolyzable functional group in five typical vegetable widely consumed in Republic of Korea is described. The sample clean-up was carried out according to the method of Food Code No. 83 established by the Korea Food and Drug Administration (KFDA). Zorbox XDB-C(18) column was selected for the analysis because of the best peak separation. The LC mobile phase consisted of water and 5 mm methanolic ammonium formate, which resulted in a peak shape with good symmetry at each run. Tandem mass spectroscopic (MS/MS) experiments were performed in ESI positive mode and the multiple reaction monitoring modes. A conventional matrix effect was modified to more comprehensive form 100gamma(ij) (%). A high matrix effect (<-30%) was detected for the seven polar pesticides, namely thiamethoxam, clothianidin, acetamiprid, aldicarb, thiacloprid, pirimicarb and methabenzthiazuron. The limits of detection were in the range of 0.1-8.1 microg/kg, indicating a good sensitivity. Most of the recoveries ranged from 70 to 131% with RSDs