Photo-degradation dynamics of five neonicotinoids: Bamboo vinegar as a synergistic agent for improved functional duration.

The effects of photo-degradation on the utilization of pesticides in agricultural production has been investigated. Various influencing factors were compared, with results showing that the initial pesticide concentration, light source, water quality and pH possessed different effects on neonicotinoids photo-degradation. The initial concentration and pH were found to be most critical effects. The photo-degradation rate decreased by a factor of 2-4 when the initial concentration increased from 5 mg L-1 to 20 mg L-1, particularly for acetamiprid and imidacloprid. The photo-degradation pathways and products of the five neonicotinoids were also investigated, with similar pathways found for each pesticide, except for acetamiprid. Degradation pathways mainly involved photo-oxidation processes, with products identified using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) found to be consistent with literature reported results. Bamboo vinegar exerted a photo-quenching effect on the neonicotinoids, with an improved efficiency at higher vinegar concentrations. The photo-quenching rates of thiamethoxam and dinotefuran were 381.58% and 310.62%, respectively, when a 30-fold dilution of vinegar was employed. The photo-degradation products in bamboo vinegar were identical to those observed in methanol, with acetic acid being the main factor influencing the observed quenching effects.

Structures and bioactivities of seven flavonoids from Osmanthus fragrans 'Jinqiu' essential oil extraction residues.

Osmanthus fragrans are well-known for their fragrance, but it is wasteful if to discard O. fragrans flower after extracting their essential oils. In this paper, we found that O. fragrans flower residues were rich in flavonoids. Six flavonoids and one phenylethanoid glycoside were isolated from the ethanol extract of O. fragrans flower residues, identified as quercetin (1), rutin (2), verbascoside (3), genistin (4), kaempferol (5), isorhamnetin (6) and naringin (7). In bioactivity study, kaempferol (IC50 = 1.43 µg/mL) showed the best anti-inflammatory activity. Isorhamnetin, quercetin, kaempferol, verbascoside and rutin (the values of IC50 were 18.30, 11.05, 16.88, 20.21 and 22.76 µg/mL, respectively) showed excellent DPPH free radical scavenging activity. Verbascoside performed relatively well at inhibiting the growth of both CT26 colonic carcinoma cells (IC50 = 46.87 µg/mL) and HepG2 hepatocarcinoma cells (IC50 = 30.58 µg/mL). In addition, quercetin and kaempferol showed strong anti-proliferation activity against HepG2 cells.

Metabolic Engineering of Escherichia coli for Astragalin Biosynthesis.

Astragalin (kaempferol 3-O-glucoside) is used as a standard to assess the quality of Radix astragali and has exhibited a number of biological properties. In this work, we screened several UDP-dependent glycosyltransferases (UGT) for their potential as efficient biocatalysts for astragalin synthesis. The highest astragalin production with 285 mg/L was detected in the recombinant strain expressing UGT from Arabidopis thaliana (AtUGT78D2). To further improve astragalin production, an efficient UDP-glucose synthesis pathway was reconstructed in the recombinant strain by introducing sucrose permease, sucrose phosphorylase, and uridylyltransferase. On the basis of those results, a recombinant strain, BL21-II, was constructed to produce astragalin. By optimizing conversion conditions, astragalin production was increased from 570 to 1708 mg/L. The production was scaled up using a fed-batch fermentation, and maximal astragalin production was 3600 mg/L, with a specific productivity of 150 mg/L/h after 24 h incubation and a corresponding molar conversion of 91.9%, the highest yield reported to date.

GC×GC-TOFMS Analysis of Essential Oils Composition from Leaves, Twigs and Seeds of Cinnamomum camphora L. Presl and Their Insecticidal and Repellent Activities.

Interest in essential oils with pesticidal activity against insects and pests is growing. In this study, essential oils from different parts (leaves, twigs and seeds) of Cinnamomum camphora L. Presl were investigated for their chemical composition, and insecticidal and repellent activities against the cotton aphid. The essential oils, obtained by hydrodistillation, were analyzed by GC×GC-TOFMS. A total of 96 components were identified in the essential oils and the main constituents found in the leaves and twigs were camphor, eucalyptol, linalool and 3,7-dimethyl-1,3,7-octatriene. The major components found in the seeds were eucalyptol (20.90%), methyleugenol (19.98%), linalool (14.66%) and camphor (5.5%). In the contact toxicity assay, the three essential oils of leaves, twigs and seeds exhibited a strong insecticidal activity against cotton aphids with LC50 values of 245.79, 274.99 and 146.78 mg/L (after 48 h of treatment), respectively. In the repellent assay, the highest repellent rate (89.86%) was found in the seed essential oil at the concentration of 20 µL/mL after 24 h of treatment. Linalool was found to be a significant contributor to the insecticidal and repellent activities. The results indicate that the essential oils of C. camphora might have the potential to be developed into a natural insecticide or repellent for controlling cotton aphids.

Variations in chemical fingerprints and major flavonoid contents from the leaves of thirty-one accessions of Hibiscus sabdariffa L.

The leaves of Hibiscus sabdariffa L. have been used as traditional folk medicines for treating high blood pressure and fever. There are many accessions of H. sabdariffa L. throughout the world. To assess the chemical variations of 31 different accessions of H. sabdariffa L., fingerprinting analysis and quantitation of major flavonoids were performed by high-performance liquid chromatography (HPLC). The HPLC method was validated for linearity, sensitivity, precision, repeatability and accuracy. A quadrupole-time-of-flight mass spectrometry (Q-TOF-MS) was applied for the characterization of major compounds. A total of 9 compounds were identified, including 6 flavonoids and 3 phenolic acids. In the fingerprint analysis, similarity analysis (SA) and principal component analysis (PCA) were used to differentiate the 31 accessions of H. sabdariffa L. Based on the results of PCA and SA, the samples No. 15 and 19 appeared much different from the main group. The total content of five flavonoids varied greatly among different accessions, ranging from 3.35 to 23.30 mg/g. Rutin was found to be the dominant compound and the content of rutin could contribute to chemical variations among different accessions. This study was helpful to understand the chemical variations between different accessions of H. sabdariffa L., which could be used for quality control. © 2015 The Authors Biomedical Chromatography Published by John Wiley & Sons Ltd.

Two new compounds from the leaves of Indocalamus latifolius.

Two new compounds, erythro-syringylglycerol-9-O-trans-4-hydroxycinnamate 7-O-ß-d-glucopyranoside (1) and indocalatin A (2), together with three known ones, 5,7,3'-trihydroxy-6-C-ß-d-digitoxopyranosyl-4'-O-ß-d-glucopyranosyl flavonoid (3), 5,4'-dihydroxy-3',5'-dimethoxy-7-O-[ß-d-apiose-(1→2)]-ß-d-glucopyranosyl flavonoid (4), and tricin-6-C-ß-boivinopyranosyl-8-C-ß-glucopyranoside (5), were isolated from the 95% EtOH extract of Indocalamus latifolius leaves. Their molecular structures were determined by UV, IR, HRESIMS, CD, and 1D and 2D NMR data analyses.

Chemical Constituents and Antibacterial Properties of Indocalamus latifolius McClure Leaves, the Packaging Material for "Zongzi".

The glutinous rice dumpling named "Zongzi" in Chinese is a type of traditional food that is popular in East Asian countries. "Zongzi" is made of glutinous rice and wrapped in the leaves of Indocalamus latifolius McClure as the packaging material. Four new compounds, latifoliusine A (2), (7S,8R) syringylglycerol-8-O-4'-sinapyl ether 4-O-ß-d-glucopyranoside (7), (7S,8S) syringylglycerol-8-O-4'-sinapyl ether 7-O-ß-d-glucopyranoside (8), and (7R,8S) syringylglycerol-8-O-4'-sinapyl ether 7-O-ß-d-glucopyranoside (10), along with six known compounds (1, 3-6 and 9) were isolated from I. latifolius McClure leaves. The structures and relative configurations of the compounds were determined by detailed spectroscopic analysis, high-resolution electrospray ionization mass spectroscopy (HRESIMS), heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser enhancement (NOE) and circular dichroism (CD). All of the isolated compounds were screened for their antibacterial activities in vitro. The results indicated that apigenin 6-C-α-l-arabinopyranosyl-8-C-ß-d-glucopyranoside (5) and apigenin 7-O,8-C-di-glucopyranoside (6) have antibacterial activities against four bacterial strains (Staphylococcus aureus, Bacillus thuringiensis, Escherichia coli and Pseudomonas solanacearum).

Enantiomeric determination of four diastereoisomeric oxyneolignans from Bambusa tuldoides Munro.

INTRODUCTION: Bambusa tuldoides Munro, a bamboo species, is used as a health food, dietary supplement and folk medicine in China, and produces lignans that can be used to supplement other natural sources. OBJECTIVE: To simultaneously separate eight stereoisomers of a particular type of oxyneolignan by chiral chromatography. METHODS: Ninety-five per cent ethanol extracts of B. tuldoides Munro were analysed using HPLC/UV with a chiral column. The structures and configurations of isolated compounds were elucidated using NMR and circular dichroism (CD). RESULTS: Four diastereoisomers were characterised and given the names oxyneolignans A, B, C and D. Furthermore, each oxyneolignan occurred as a pair of enantiomers. The oxyneolignans A-D consisted of the erythro-diastereoisomer of oxyneolignan at C7 and C8. CONCLUSION: The chiral chromatography combined with the analysis techniques of NMR and CD reported here were reliable methods for discovering and separating the enantiomers.

The occurrence and distribution of antibiotics in Lake Chaohu, China: seasonal variation, potential source and risk assessment.

The distribution and seasonal variation of fifteen antibiotics belonging to three classes (sulfonamides, fluoroquinolones and tetracyclines) were investigated in Lake Chaohu, China. The concentrations of the selected antibiotics in the surface water, eight major inflowing rivers and sewage treatment plant (STP) samples were analyzed by UPLC-MS/MS. The results indicated that sulfamethoxazole and ofloxacin were the predominant antibiotics, with maximum concentrations of 95.6 and 383.4ngL(-1), respectively, in the river samples. In Lake Chaohu, the western inflowing rivers (the Nanfei and Shiwuli Rivers) were the primary import routes for the antibiotics, and the domestic effluent from four STPs were considered the primary source of the antibiotics. The level of antibiotics in Lake Chaohu clearly varied with seasonal changes, and the highest detectable frequencies and mean concentrations were found during the winter. The quality of water downstream of Lake Chaohu was influenced by the lake, and the results of risk assessment of the antibiotics on aquatic organisms suggested that sulfamethoxazole, ofloxacin, ciprofloxacin and enrofloxacin in the surface water of Lake Chaohu and inflowing rivers might pose a high risk to algae and plants.

Antioxidant activity of leaf extracts from different Hibiscus sabdariffa accessions and simultaneous determination five major antioxidant compounds by LC-Q-TOF-MS.

Hibiscus sabdariffa has gained attention for its antioxidant activity. There are many accessions of H. sabdariffa in the world. However, information on the quantification of antioxidant compounds in different accessions is rather limited. In this paper, a liquid chromatography/quadrupole-time-of-flight mass spectrometry (LC-Q-TOF-MS) method for simultaneous determination of five antioxidant compounds (neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, rutin, and isoquercitrin) in H. sabdariffa leaves was developed. The method was validated for linearity, sensitivity, precision, repeatability and accuracy. The validated method has been successfully applied for determination of the five analytes in eight accessions of H. sabdariffa. The eight accessions of H. sabdariffa were evaluated for their antioxidant activities by DPPH free radical scavenging assay. The investigated accessions of H. sabdariffa were rich in rutin and exhibited strong antioxidant activity. The two accessions showing the highest antioxidant activities were from Cuba (No. 2) and Taiwan (No. 5). The results indicated that H. sabdariffa leaves could be considered as a potential antioxidant source for the food industry. The developed LC-Q-TOF-MS method is helpful for quality control of H. sabdariffa.

[Simultaneous determination of four flavone C-glycosides in Phyllostachys edulis leaves by high-performance liquid chromatography with ultraviolet spectrometry].

High-performance liquid chromatography with ultraviolet spectrometer (HPLC-UV) was used to simultaneously detect the four flavone C-glycosides, i. e. orientin, isoorientin, vitexin and isovitexin. Analytes were separated with Waters XTerra MS C18 column (250 mm x 4.6 mm, 5 µm) using acetonitrile and 0.5% (φ) formic acid as mobile phase. The flow rate was set at 1.0 mL · min(-1) with the column temperature at 30 °C, and the detection wavelength was 360 nm. The calibration curve was linear over the concentration range of 0.1-10.0 mg · L(-1) for the mixed standard solution. Analytes were separated in 22 minutes, and the relative standard deviation values were all above 0.999. LOD values of standards were found to be between 0.03 and 0.07 mg · L(-1), and LOQ values were in the range of 0.04-0.08 mg · L(-1). After comparing the spectra (240-400 nm) of four flavone C-glycosides in mixed standards and the final product purified by macroporous resin, respectively, the curve shape and characteristic ultraviolet absorption wavelength of each flavone C-glycoside including orientin, isoorientin, vitexin and isovitexin were fitted well. The bamboo leaves sample was extracted by ethanol under reflux, and then partitioned with water and petroleum ether. The aqueous phase was added onto macroporous resin (AB-8), and the fraction of ethanol-water (40%, φ) was concentrated. It was found that the contents of orientin, isoorientin, vitexin and isovitexin relative to the fraction of ethanol- water were 13.73, 49.68, 7.85 and 30.70 mg · g(-1), respectively. In addition, the average recovery of the four flavone C-glycosides ranged from 34.90% to 87.64% with RSD values from 0.41% to 10.83%. The results showed that bamboo leaves sample had good stability and repeatability. The new method was used to analyze the four flavone C-glycosides quickly and provide quality control for commercial products.

Two new compounds from the dry leaves of Pleioblastus amarus (Keng) keng f.

Two new compounds, xylitol 1-O-(6'-O-p-hydroxylbenzoyl)-glucopyranoside (1) and bambulignan B (2), together with three known ones gastrodin (3), glucovanillin (4), and rel-(7S,7'R,8R,8'S)-4,4'-dihydroxy-3,3',5,5'-tetramethoxy-7,7'-epoxyligna-9,9'-diol-9(or)9'-O-ß-glucopyranoside (5), were isolated from the 95% EtOH extract of the dry leaves of Pleioblastus amarus (Keng) keng f. Their structures were determined by UV, IR, HR-ESI-MS, CD, and 1D and 2D NMR data analyses as well as GC experiments.

Simultaneous determination of 12 coumarins in bamboo leaves by HPLC.

A simple, rapid, and sensitive HPLC-UV method was developed for qualitative and quantitative analysis of 12 coumarin compounds (skimin, scopolin, scopoletin, umbelliferone, 6,7-dimethoxycoumarin, coumarin, psoralen, xanthotoxin, 5,7-dimethoxycoumarin, pimpinellin, imperatorin, and osthole) in bamboo leaves. The samples were extracted with ethanol-water (70 + 30, v/v) by ultrasonication and purified by Florisil SPE. The method was validated for linearity, LOD, LOQ, accuracy, precision, and recovery. The standard curves in the corresponding ranges had good linearity. LOD was at the range of 0.19 to 0.85 mglkg and LOQ 0.64 to 2.82 mg/kg. The values of RSD for accuracy and intraday and interday precision were less than 3%, except for 6,7-dimethoxycoumarin. Recoveries from spiked samples at 30, 20, and 10 mg/kg in Dendrocalamus giganteus Munro were higher than 70%, except for scopoletin, 6,7-dimethoxycoumarin, and coumarin. The method was validated using field-collected samples taken from Beijing and Changning Counties, SiChuan, China. Six coumarins, namely, skimin, scopolin, scopoletin, umbelliferone, coumarin, and pimpinellin, were found in the extracts of 11 species of bamboo leaves. The concentrations of total coumarins were in the range of 8.67 to 99.2 mg/kg. The maximum concentration of total coumarins was found in Bambusa pervariabilis, and the minimum was in

Fragmentation characterization and differentiation of isomeric diglycosyl flavonoids using ultra-high-performance liquid chromatography electrospray ionization quadrupole time-of-flight tandem mass spectrometry in negative ion mode.

Flavonoids exhibit a wide range of biological activities and the fragmentation characterization and differentiation of isomeric diglycosyl flavonoids is an important area of research. In this study, ultra-high-performance liquid chromatography electrospray ionization quadrupole time-of-flight tandem mass spectrometry was used to identify two pairs of isomeric diglycosyl flavonoids: naringin/narirutin and neohesperidin/hesperidin. The two pairs of flavonoids were identified by product ion tandem mass spectra of the precursor ions [M-H]-. The results showed that characteristic product ions distinguishing flavonoids glycosylated with rhamnosyl-(alpha1 --> 2)-glucosyl from isomeric flavonoids glycosylated with rhamnosyl-(alpha1 --> 6)-glucosyl were the precursor ion [M-H]- and its characteristic product ions Y0- and [0.2X0-H]-.

Isolation and identification of lignans from Caulis Bambusae in Taenia with antioxidant properties.

Caulis Bambusae in Taenia is a medicinal preparation from Bambusa tuldoides Munro consisting of skinless slices of the stem (bamboo shavings) and used as a traditional health food in tea, wine, and soup in Asia. Three novel lignans, (-)-7'-epi-lyoniresinol 4,9'-di-O-ß-D-glucopyranoside (7), (-)-lyoniresinol 4,9'-di-O-ß-D-glucopyranoside (8), bambulignan A (10), and seven known lignan compounds (1-6 and 9) were isolated from Caulis Bambusae in Taenia. The structures of the lignans were determined by detailed spectroscopic analysis (HRESIMS, HSQC, HMBC, NOE). All the isolated lignans were tested for antioxidant activities by DPPH and FARP assays. The results showed that the compounds (+)-lyoniresinol 9'-O-ß-D-glucopyranoside (1) and (-)-7'-epi-lyoniresinol 9'-O-ß-D- glucopyranoside (9) have strong free radical scavenging activity and reducing power.

TLC screening for antioxidant activity of extracts from fifteen bamboo species and identification of antioxidant flavone glycosides from leaves of Bambusa. textilis McClure.

Interest in the antioxidant activity of bamboo leaves is growing. To discover new sources of natural antioxidants, a TLC bioautography method combined with a new image processing method was developed to evaluate the antioxidant activity of leaf extracts from 15 different species of bamboo. The results showed that the methanolic extract of Bambusa. textilis McClure possessed the highest antioxidant activity among the selected bamboo species. To rapidly identify the antioxidant compounds, the crude extract of B. textilis McClure was analysed by HPLC-UV, and HPLC-micro-fractionation of the extract was carried out. Based on TLC bioautography-guided fractionation, three antioxidant fractions were isolated from B. textilis McClure by preparative chromatography. These three antioxidant compounds were identified as isoorientin 4''-O ß-D-xylopyranoside, isoorientin 2''-O-α-L-rhamnoside and isoorientin according to their UV, MS, and NMR data. The proposed TLC screening method could therefore be an easy way to evaluate the antioxidant activity of bamboo leaves, and the results achieved should prove very helpful for promoting their utilization, as B. textilis McClure can be considered a promising plant source of natural antioxidants.

Screening and analysis of the potential bioactive components in rabbit plasma after oral administration of hot-water extracts from leaves of Bambusa textilis McClure.

Bambusa textilis McClure is a traditional Chinese medicinal plant belonging to the Bambusoideae subfamily and used to treat chronic fever and infectious diseases. To investigate the bioactive compounds absorbed in the rabbit blood after oral administration of hot-water extracts from the leaves of B. textilis McClure, a validated chromatographic fingerprint method was established using LC-Q-TOF-MS. Twenty compounds in bamboo leaves and three potential bioactive compounds in rabbit plasma were detected. Of the twenty detected compounds in vitro, fifteen of which were tentatively identified either by comparing the retention time and mass spectrometry data with that of reference compounds or by reviewing the literature. Three potential bioactive compounds, including (E)-pcoumaric acid, (Z)-p-coumaric acid, and apigenin-8-C-ß-D-(2"-O-α-L-rhamnosyl)-glucopyranoside, were detected in both the leaves of B. textilis McClure and rabbit plasma. Of the three compounds, apigenin-8-C-ß-D-(2"-O-α-L-rhamnosyl)glucopyranoside was identified based on its UV, MS, and NMR spectra. This study provides helpful chemical information for further pharmacology and active mechanism research on B. textilis McClure.

Rapid Screening for Flavone C-Glycosides in the Leaves of Different Species of Bamboo and Simultaneous Quantitation of Four Marker Compounds by HPLC-UV/DAD.

A strategy for analyzing flavone C-glucosides in the leaves of different species of bamboo was developed. Firstly, the flavone C-glycosides were extracted from the bamboo leaves (51 species in 17 genera) with methanol and chromatographed on silica gel 60 plates in automatic developing chamber (ADC2), and a qualitative survey using simple derivatization steps with the NP reagent was carried out. The flavone C-glycosides were found in 40 of 51 species of bamboo examined. Secondly, an HPLC method with photodiode array and multiple wavelength detector was optimized and validated for the simultaneous determination of flavone C-glycosides, including isoorientin, isovitexin, orientin, and vitexin in the leaves of three species of bamboo and the flavone C-glycosides were confirmed by LC/MS. The optimized HPLC method proved to be linear in the concentration range tested (0.2-100 µg/mL, r(2) ≥ 0.9997), precise (RSD ≤ 1.56%), and accurate (88-106%). The concentration ranges of isoorientin, isovitexin, orientin, and vitexin in three bamboo leaves samples were 1.00-2.78, 0-0.31, 0-0.07, and 0.20-0.68 mg/g, respectively. The proposed method was validated to be simple and reliable and can be a tool for quality control of bamboo leaf extract or its commercial products.

[Comparative analysis of volatile fractions in Polygonati rhizoma and its processed products by GC-MS].

OBJECTIVE: To conduct comparative study on the volatile components from Polygonati Rhizoma during processing. METHOD: Volatile oil was obtained from Polygonati Rhizoma by steam distillation (SD). Volatile components were concentrated by a purge and trap-thermal desorption (P&T-TD) method, and analyzed with gas chromatography-mass spectrometry (GC-MS), which were comparative by analyzed with the method of SD-GC-MS simultaneously. RESULT: The change in quantity and quality of volatile components in pre and post processed Polygonati Rhizoma were observed. Fifty-one compounds were checked out with SD-GC-MS, while 11 compounds with P&T-TD-GC-MS. CONCLUSION: This study is useful to illustrate the mechanism of decreasing toxicity and stimulating components after being processed.

Development and validation of an HPTLC method for simultaneous quantitation of isoorientin, isovitexin, orientin, and vitexin in bamboo-leaf flavonoids.

A simple HPTLC method has been developed for the simultaneous determination of isoorientin, isovitexin, orientin, and vitexin, both pure and in commercial samples of bamboo-leaf flavonoids. The flavone C-glycosides, including isoorientin, isovitexin, orientin, and vitexin, were extracted from bamboo-leaf flavonoids with methanol and chromatographed on silica gel 60 plates in an automatic developing chamber with tetrahydrofuran-toluene-formic acid-water (16 + 8 + 2 + 1, v/v/v/v) mobile phase. Quantitation was obtained with UV detection at 350 nm. Polynomial calibration plots were constructed in the concentration range 200-1200 ng/zone for isoorientin, 100-600 ng/zone for isovitexin, 160-960 ng/zone for orientin, and 30-360 ng/zone for vitexin with good correlation coefficients (r > or = 0.9995). The method was validated for precision (interday and intraday), repeatability, and accuracy. Accuracy of the method was evaluated by a recovery study conducted at three different levels, and the average recovery was found to be 93.95% for isoorientin, 95.30% for isovitexin, 99.79% for orientin, and 100.46% for vitexin. The proposed HPTLC method for estimation of isoorientin, isovitexin, orientin, and vitexin was found to be simple, precise, specific, and accurate and can be used for manufacturing QC of bamboo-leaf flavonoids or for governmental regulatory purposes.