Rapid Quantitative Detection of Deltamethrin in Corydalis yanhusuo by SERS Coupled with Multi-Walled Carbon Nanotubes.

With the increase in demand, artificially planting Chinese medicinal materials (CHMs) has also increased, and the ensuing pesticide residue problems have attracted more and more attention. An optimized quick, easy, cheap, effective, rugged and safe (QuEChERS) method with multi-walled carbon nanotubes as dispersive solid-phase extraction sorbents coupled with surface-enhanced Raman spectroscopy (SERS) was first proposed for the detection of deltamethrin in complex matrix Corydalis yanhusuo. Our results demonstrate that using the optimized QuEChERS method could effectively extract the analyte and reduce background interference from Corydalis. Facile synthesized gold nanoparticles with a large diameter of 75 nm had a strong SERS enhancement for deltamethrin determination. The best prediction model was established with partial least squares regression of the SERS spectra ranges of 545~573 cm-1 and 987~1011 cm-1 with a coefficient of determination (R2) of 0.9306, a detection limit of 0.484 mg/L and a residual predictive deviation of 3.046. In summary, this article provides a new rapid and effective method for the detection of pesticide residues in CHMs.

Effective preparation of magnetic molecularly imprinted polymer nanoparticle for the rapid and selective extraction of cyfluthrin from honeysuckle.

Cyfluthrin is a widely used pesticide. In this study, a sensitive and efficient magnetic molecularly imprinted polymer (MMIP) was prepared by surface molecular imprinting, which used functionalized Fe3O4 particles as magnetic cores. Cyfluthrin was extracted and enriched using magnetic molecularly polymer for analyzing pesticide residue of Chinese herbal medicines. The crystal type, microstructure, particle size, saturation magnetization, and characteristic functional groups of the synthesized MMIPs were analyzed by analysis equipment. The results of isothermal adsorption and kinetic adsorption indicated that MMIPs reached adsorption equilibrium at 30 min, with a maximum capacity of 4.9 mg g-1, which had good adsorption performance, while selective adsorption experiments showed that MMIPs had higher affinity for cyfluthrin. Under the optimized conditions, the limit of detection (LOD) and the limit of quantification (LOQ) were 32.987 ng ml-1 and 109.955 ng ml-1, respectively. And linear range (30-3000ng ml-1) of cyfluthrin with correlation coefficient R2=0.9979, and MMIPs were used in honeysuckle, the recoveries were 91.5%∼97.2%, and RSD was 5.35%∼8.32% (n = 3). It is indicated that the magnetic molecularly imprinted polymer can be used as an effective material for the specific separation of cyfluthrin from honeysuckle.

Centaurea microcarpa Coss. & Dur. (Asteraceae) extracts: New cyanogenic glucoside and other constituents.

The phytochemical investigation of both chloroform and ethyl acetate extracts of Centaurea microcarpa Coss. & Dur. led to the isolation of a new cyanogenic glucoside 6'-methacrylate prunasin (3) together with seven known compounds: hydroxy-11ß,13-dihydro onopordaldehyde (1), ß-sitosterol (2), daucosterol (4), nepetin (5), prunasin (6), astragalin (7) and 7-O-ß-D-glucopyranosyl centaureidin (8). Their structures were established by spectral analysis, mainly UV, IR, ESI-MS, 1D & 2D-NMR experiments (COSY, HSQC, HMBC and ROESY).

Industrial prune processing and its effect on pesticide residue concentrations.

The aim of this study was to determine the insecticide residue processing factor (PF) from plums to prunes and the effect of the industrial processing of prunes residue concentrations. Our results show an increase of insecticide concentrations during plum dehydration that is explained by fruit water loss; however, the normalized insecticide residue concentration, based on plum dry weights to compensate dehydration, was reduced. The water washing and tenderizing of prunes produced insecticide residue reductions of 22.9 ±â€¯4.5% and 21.9 ±â€¯4.2%, respectively. PF were: 1.157, 1.872, 1.316, 0.192, 2.198, 0.775 and 0.156 for buprofezin, l-cyhalothrin, spirodiclofen, indoxacarb, acetamiprid, imidacloprid and emamectin benzoate, respectively, being directly related to water solubility, aqueous hydrolysis and degradation point and inversely related to molecular mass and melting point. In plums for the dehydrated agroindustry the final product is prunes, therefore, it is crucial to consider the PF to determine the specific preharvest interval for this important agroindustry.

New sesquiterpenoid isonitriles from three species of phyllidid nudibranchs.

Chemical investigation of the two nudibranch species Phyllidiella pustulosa and Phyllidia ocellata collected in Queensland, Australia, provided new stereoisomers of 4-isocyano-9-amorphene (1) and of 10-isocyano-4-amorphene (2), respectively. A specimen of Phyllidia picta collected from Bali, Indonesia, contained the axane sesquiterpenoids pictaisonitrile-1 (3) and pictaisonitrile-2 (4). The planar structures were elucidated using 1D and 2D NMR spectroscopy, while relative configurations were established using NOESY correlations, coupling constant data, and comparison with literature data.

Aqueous ozone solutions for pesticide removal from potatoes.

The presence of pesticide residues in potatoes is of concern because of the potential impact to human health due to the high consumption of this vegetable. In this study, aqueous solutions with and without ozone saturation as postharvest wash treatment at pH 4.0, 7.0, and 9.0 were tested to remove chlorothalonil from potatoes. The method used for pesticide analysis has been validated, presenting recovery values of 94-103%, with variations in the repeatability coefficients of ≤10.6%, and a quantification limit of 0.05 mg kg-1 Regardless of pH, treatment with aqueous ozone solutions removed 70-76% of the pesticide present in the potato. In the no-ozone treatments, the percentage average removal of chlorothalonil residues in potatoes was only 36%. Over 24 days of storage, the quality of potatoes washed with aqueous ozone solutions was not significantly different from those washed with pure water.

γ-Hydroxynitrile glucosides from the seeds of Prinsepia utilis.

γ-Hydroxynitrile glucosides (prinsepicyanosides A-E) were isolated alongside 11 known compounds from seeds of Prinsepia utilis Royle. Their structures were determined by detailed analysis of NMR and MS spectroscopic data. The relative configuration of prinsepicyanoside C was established by Cu-Kα X-ray crystallography. Prinsepicyanoside A, osmaronin, and 4-(hydroxylmethyl)-5H-furan-2-one exhibited borderline antibacterial activity against Salmonella gallinarum, Vibrio parahaemolyticus, and Vibrio cholera with MIC values of 30.1, 20.7, and 22.8µg/mL, respectively.

Simultaneous determination of sulphoraphane and sulphoraphane nitrile in Brassica vegetables using ultra-performance liquid chromatography with tandem mass spectrometry.

INTRODUCTION: Several analytical methods exist for the determination of sulphoraphane or sulphoraphane nitrile from biological matrices and plant extracts. However, no UPLC-MS/MS method exists for the simultaneous detection of both. OBJECTIVE: To develop and validate an UPLC-MS/MS method for the simultaneous analysis of sulphoraphane and sulphoraphane nitrile from Brassica oleracea L. ssp. italica METHODS: This method was developed utilising an Acquity BEH C8 column with gradient elution combined with tandem mass spectrometry, using positive electrospray ionisation in multiple reaction monitoring mode. RESULTS: The retention times for sulphoraphane and sulphoraphane nitrile were 0.4 and 0.6 min respectively, and total run time was 3 min. The method was validated for linearity, sensitivity, precision, accuracy, matrix effects and recovery. The method was employed to determine glucoraphanin hydrolysis products in broccoli and the predominant product was found to vary depending on the variety tested. It was also applied to the accurate determination of sulphoraphane and sulphoraphane nitrile in broccoli samples hydrolysed under different conditions. It was observed that the formation of sulphoraphane and sulphoraphane nitrile was influenced by the temperature of the reaction. CONCLUSION: The validated UPLC-MS/MS method for simultaneous detection of sulphoraphane and sulphoraphane nitrile was shown to be applicable to broccoli plants and is expected to be applicable to other cruciferous sources.

Quantitative analysis of amygdalin and prunasin in Prunus serotina Ehrh. using (1) H-NMR spectroscopy.

INTRODUCTION: Prunus serotina is native to North America but has been invasively introduced in Europe since the seventeenth century. This plant contains cyanogenic glycosides that are believed to be related to its success as an invasive plant. For these compounds, chromatographic- or spectrometric-based (targeting on HCN hydrolysis) methods of analysis have been employed so far. However, the conventional methods require tedious preparation steps and a long measuring time. OBJECTIVE: To develop a fast and simple method to quantify the cyanogenic glycosides, amygdalin and prunasin in dried Prunus serotina leaves without any pre-purification steps using (1) H-NMR spectroscopy. METHODS: Extracts of Prunus serotina leaves using CH3 OH-d4 and KH2 PO4 buffer in D2 O (1:1) were quantitatively analysed for amygdalin and prunasin using (1) H-NMR spectroscopy. Different internal standards were evaluated for accuracy and stability. The purity of quantitated (1) H-NMR signals was evaluated using several two-dimensional NMR experiments. RESULTS: Trimethylsilylpropionic acid sodium salt-d4 proved most suitable as the internal standard for quantitative (1) H-NMR analysis. Two-dimensional J-resolved NMR was shown to be a useful tool to confirm the structures and to check for possible signal overlapping with the target signals for the quantitation. Twenty-two samples of P. serotina were subsequently quantitatively analysed for the cyanogenic glycosides prunasin and amygdalin. CONCLUSION: The NMR method offers a fast, high-throughput analysis of cyanogenic glycosides in dried leaves permitting simultaneous quantification and identification of prunasin and amygdalin in Prunus serotina.

[Chemical constituents from the linseed meal].

Ten compounds were isolated from the 70% ethanol extract of linseed meal (Linum usitatissimum L) through a combination of various chromatographic techniques, including silica gel, macroporous adsorbent resin, Sephadex LH-20, and preparative HPLC. On the basis of spectroscopic data analysis, they were elucidated as 1-methylethyl-2-O-beta-D-glucopyranosyl-(1" --> 6')-beta-D-glucopyanoside (1), linustatin (2), neolinustatin (3), lotaustralin (4), linamarin (5), deoxyguanosine (6), deoxyadenosine (7), (+)-pinoresinol-4'-O-beta-D-glucopyranoside (8), 4-O-beta-D-glucopyranosylvanillyl alcohol (9) and tachioside (10), separately. Among them, compound 1 is a new compound, and compounds 6, 8 and 10 were isolated from the linseed meal for the first time.

The rare cyanogen proteacin, and dhurrin, from foliage of Polyscias australiana, a tropical Araliaceae.

The tyrosine-derived cyanogenic di-glucoside proteacin and related mono-glucoside dhurrin were identified as the cyanogens in foliage of the tropical tree species Polyscias australiana, present in the approximate ratio 9:1. To date cyanogenic glycosides have not been characterised from the Araliaceae or the Apiales. Concentrations of cyanogenic glycosides varied significantly between plant parts and with leaf age, with the highest concentrations in young emerging leaves (mean 2217.1 µg CN g(-1) dry wt), petioles (rachis; 1487.1 µg CN g(-1) dry wt) and floral buds (265.8 µg CN g(-1) dry wt). Between 2% and 10% of nitrogen in emerging leaves and petioles was present as cyanogenic glycosides. With the exception of floral buds, all tissues apparently lack a specific cyanogenic ß-glucosidase to catalyse the first step in the breakdown of these cyanogenic glycosides. Only with the addition of emulsin, an exogenous non-specific ß-glucosidase from almonds, were high concentrations of cyanogenic glycosides detected, as much as 20-fold greater than the low to negligible cyanogenic glycoside concentrations determined in the absence of exogenous enzyme. High concentrations of cyanogens in young tissues may confer protection, but may also be a nitrogen source during leaf expansion.

Antioxidative polyphenols from Nigerian mistletoe Loranthus micranthus (Linn.) parasitizing on Hevea brasiliensis.

Two new phenolic glycosides, linamarin gallate (1) and walsuraside B (2), together with nine known compounds, catechin (3), epicatechin (4), epicatechin 3-O-gallate (5), epicatechin 3-O-(3-O-methyl)gallate (6), epicatechin 3-O-(3,5-O-dimethyl)gallate (7), epicatechin 3-O-(3,4,5-O-trimethyl)gallate (8), quercetin 3-O-ß-d-glucopyranoside (9), rutin (10), and peltatoside (11), were isolated from the leafy twigs of Nigerian mistletoe Loranthus micranthus (Linn.) parasitic on Hevea brasiliensis. Compound 1 was characterized as an unusual cyanogenic glycoside, while compound 8 was isolated for the first time from a natural source. This is the first report of a cyanogenic glycoside from mistletoes. The structures of the new compounds were unambiguously elucidated by 1D ((1)H, (13)C), 2D NMR (COSY, HSQC, and HMBC) and by mass spectroscopy. The antioxidant activities of the isolated compounds (1-11) were evaluated using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) assay.

Chemical constituents of Saniculiphyllum guangxiense.

The first phytochemical investigation on Saniculiphyllum guangxiense resulted in the isolation of two new triterpenoids, 16ß-hydroxybryodulcosigenin (3) and 3α-O-feruloylolean-12-en-27-oic acid (6), together with six known compounds, menisdaurin (1), purshianin (2), oleanolic acid (4), 3ß-hydroxyolean-12-en-27-oic acid (5), ß-sitosterol (7), and daucosterol (8), which were characterized by extensive spectroscopic analyses and in one case by X-ray diffraction. According to this primary investigation, S. guangxiense is rich in nitrile glucosides and triterpenoids, of which menisdaurin (1; 0.06%) and purshianin (2; 0.015%) are the main constituents. Compounds 1-6 were assayed for their anti-hepatitis B virus (HBV) activities against the secretion of HBsAg and HBeAg, as well as HBV DNA replication on Hep G 2.2.15 cell line in vitro. The most active compound, menisdaurin (1), inhibits HBV DNA replication with an IC(50) value of 0.32 mM (SI>11.97).

Rubber (Hevea brasiliensis) seed oil toxicity effect and Linamarin compound analysis.

BACKGROUND: The lipid fraction of rubber (Hevea brasiliensis (kunth. Muell)) seed was extracted and analyzed for toxicological effect. The toxicological compound such as linamarin in rubber seed oil (RSO) extracted using different solvents, such as hexane (RSOh), mixture of chloroform + methanol (RSOchl+mth) and ethanol (RSOeth) were also studied. Various methods analysis such as Fourier transforms infrared spectroscopy (FTIR) and colorimetric methods were carried out to determine the present of such compounds. RESULTS: FTIR spectrum of RSO did not show any presence of cyanide peak. The determination of cyanide by using colorimetric method was demonstrated no response of the cyanide in RSO and didn't show any colored comparing with commercial cyanide which observed blue color. The results showed that no functional groups such as cyanide (C ≡ N) associated with linamarin were observed. Toxicological test using rats was also conducted to further confirm the absence of such compounds. RSO did not show any toxic potential to the rats. Bioassay experiments using shrimps had been used as test organisms to evaluate the toxicity of linamarin extract from RSO(h,) RSO(chl+mth) and RSO(eth) and LC50 were found to be (211.70 %, 139.40 %, and 117.41 %, respectively). CONCLUSIONS: This can be attributed no hazardous linamarin were found in RSO.

An approach to the chemotaxonomic differentiation of two European dog's mercury species: Mercurialis annua L. and M. perennis L.

Mercurialis annua and M. perennis are medicinal plants used in complementary medicine. In the present work, analytical methods to allow a chemotaxonomic differentiation of M. annua and M. perennis by means of chemical marker compounds were established. In addition to previously published compounds, the exclusive presence of pyridine-3-carbonitrile and nicotinamide in CH(2) Cl(2) extracts obtained from the herbal parts of M. annua was demonstrated by GC/MS. Notably, pyridine-3-carbonitrile was identified for the first time as a natural product. Further chromatographic separation of the CH(2) Cl(2) extracts via polyamide yielded a MeOH fraction exhibiting a broad spectrum of side-chain saturated n-alkylresorcinols. While the n-alkylresorcinol pattern was similar for both plant species, some specific differences were observed for particular n-alkylresorcinol homologs. Finally, the investigation of H(2) O extracts by LC/MS/MS revealed the presence of depside constituents. Whereas, in M. perennis, a mixture of mercurialis acid (=(2R)-[(E)-caffeoyl]-2-oxoglutarate) and phaselic acid (=(E)-caffeoyl-2-malate) could be detected, in M. annua solely phaselic acid was found. By comparison with synthesized enantiomerically pure (2R)- and (2S)-phaselic acids, the configuration of the depside could be determined as (2S) in M. annua and as (2R) in M. perennis.

Comparative study of different clean-up techniques for the determination of λ-cyhalothrin and cypermethrin in palm oil matrices by gas chromatography with electron capture detection.

Solid phase extraction (SPE) and dispersive solid-phase extraction (d-SPE) were compared and evaluated for the determination of λ-cyhalothrin and cypermethrin in palm oil matrices by gas chromatography with an electron capture detector (GC-ECD). Several SPE sorbents such as graphitised carbon black (GCB), primary secondary amine (PSA), C(18), silica, and florisil were tested in order to minimise fat residues. The results show that mixed sorbents using GCB and PSA obtained cleaner extracts than a single GCB and PSA sorbents. The average recoveries obtained for each pesticide ranged between 81% and 114% at five fortification levels with the relative standard deviation of less than 7% in all cases. The limits of detection for these pesticides were ranged between 0.025 and 0.05 µg/g. The proposed method was applied successfully for the residue determination of both λ-cyhalothrin and cypermethrin in crude palm oil samples obtained from local mills throughout Malaysia.

A simple analytical method for dhurrin content evaluation in cyanogenic plants for their utilization in fodder and biofumigation.

Cyanogenic plants have some potential as biocidal green manure crops in limiting several soilborne pests and pathogens. Sorghum (Sorghum bicolor (L.) Moench) and Sudangrass (Sorghum bicolor subsp. sudanense (P.) Stapf), in fact, contain the cyanogenic glucoside p-hydroxy-(S)-mandelonitrile-ß-D-glucoside (dhurrin) as a substrate of its secondary defensive system able to release hydrogen cyanide following tissue lesions due to biotic or abiotic factors. Given that dhurrin content is correlated with the biofumigant efficacy of the plants, a high dhurrin content could be a positive character for utilization of sorghum and Sudangrass as biocidal green manure plants. For chemical characterization of the available germplasm, a simple, safe, and accurate method is necessary. In this paper, a new method for dhurrin analysis, based on methanol extraction and high-performance liquid chromatography, is reported and discussed. The feasibility of this analytical procedure was tested by evaluating dhurrin level in roots and stems during cultivation of four different sorghum and Sudangrass varieties in agronomic trials performed in 2008 in the Po valley (Italy). The dhurrin content ranged from 0.16 ± 0.04 to 7.14 ± 0.32 mg g(-1) on dried matter (DM) in stems and from 1.38 ± 0.02 to 6.57 ± 0.09 mg g(-1) on DM in roots, showing statistical differences among the tested germplasms that could be linked to the efficacy of their utilization as biofumigant plants. The method also opens new perspectives for the characterization of sorgum plants as fodder, for which the presence of dhurrin is considered to be negative for its well-known toxicity.

Characterisation of galloylated cyanogenic glucosides and hydrolysable tannins from leaves of Phyllagathis rotundifolia by LC-ESI-MS/MS.

INTRODUCTION: Phyllagathis rotundifolia (Jack) Bl. (Melastomataceae) is a creeping herb found in Peninsular Malaysia and Sumatra. Traditionally, a decoction of the leaves is used in the treatment of malaria, fever and stomach ache. OBJECTIVE: To provide ESI-MS(n) data which are applicable for chemical fingerprinting of P. rotundifolia to obviate laborious isolation and purification steps. METHODOLOGY: The mass spectral data for the compounds isolated from the leaves of P. rotundifolia were obtained by liquid chromatography-electrospray ionisation tandem mass spectrometry. RESULTS: The MS fragmentation patterns were obtained for galloylated cyanogenic glucosides based on prunasin (prunasin 6'­O­gallate 1, prunasin 2',6'­di­O­gallate 2, prunasin 3',6'­di­O­gallate 3, prunasin 4',6'­di­O­gallate 4, prunasin 2',3',6'­tri­Ogallate 5, prunasin 3',4',6'­tri­O­gallate 6 and prunasin 2',3',4',6'­tetra­O­gallate 7), gallotannins (6­O­galloyl­D­glucose 8, 3,6­di­O­galloyl­D­glucose 9, 1,2,3­tri­O­galloyl­ß­D­glucose 10, 1,4,6­tri­O­galloyl­ß­D­glucose 11, 3,4,6­tri­O­galloyl­D­glucose 12, 1,2,3,6­tetra­O­galloyl­ß­D­glucose 13 and 1,2,3,4,6­penta­O­galloyl­ß­D­glucose 14), ellagitannins [6­O­galloyl­2,3­O­(S)­hexahydroxy­diphenoyl­D­glucose 15, praecoxin B 16 and pterocarinin C 17], ellagic acid derivatives (3'­O­methyl­3,4­methylenedioxyellagic acid 4'­O­ß­D­glucopyranoside 18 and 3,3',4­tri­O­methylellagic acid 4'­O­ß­D­glucopyranoside 19) and gallic acid 20 that were isolated from the leaves of P. rotundifolia. CONCLUSION: The ESI-MS(n) technique facilitates identification of galloylated cyanogenic glucosides, hydrolysable tannins and ellagic acid derivatives that were isolated from the leaves of P. rotundifolia. It yields MS(n) spectra that are useful for identification of these compounds in complex samples and permit more complete fingerprinting of plant materials.

Use of spent substrate after Pleurotus pulmonarius cultivation for the treatment of chlorothalonil containing wastewater.

Lignocellulosic materials are used as substrate for the cultivation of the edible mushroom Pleurotus pulmonarius. After two or three flushes of mushrooms, the spent substrate is discarded although it still has an important enzymatic activity that can be used for several purposes. In this study, we sought to determine the technical feasibility of using spent substrate from P. pulmonarius to degrade chlorothalonil. Reaction mixture was prepared with 6 ml of pesticide aqueous solution (2 mg active ingredient/l) and 3 ml of enzymatic extract obtained from spent P. pulmonarius substrate. The enzymatic reaction (27 °C, pH 7.4) was conducted for 1 h with sampling at 15 min intervals. The effect of storage time and temperature (freezing or refrigerating) of spent substrate and enzymatic extract, respectively, on the activity over chlorothalonil was determined. Freshly obtained spent substrate extract was able to reduce 100% of the initial concentration of chlorothalonil (2 mg/l) after 45 min of reaction. Storage time had a negative effect on the stability of the enzymatic activity: with spent substrate stored for a week, chlorothalonil concentration was reduced in 49.5% after 1 h reaction and with substrate stored for two and three weeks, the degradation efficiency decreased to 9.15% and 0%, respectively. Cooling and freezing the spent substrate extract also had a negative effect on chlorothalonil degradation.

Standardization and in vivo antioxidant activity of ethanol extracts of fruit and leaf of Piper sarmentosum.

The present study aimed to investigate standardized ethanol extracts of fruit and leaves of Piper sarmentosum for their in vivo antioxidant activity in rats using a CCl (4)-induced oxidative stress model. The standardization was based on the quantification of the markers pellitorine, sarmentine and sarmentosine by high performance liquid chromatography (HPLC), and determination of total primary and secondary metabolites. The rats, divided into 7 groups each (n = 6), were used as follows: group 1 (CCl (4), negative control), group 2 (untreated, control), groups 3 and 4 (fruit extract 250 and 500 mg/kg, respectively), groups 5 and 6 (leaf extract 250 and 500 mg/kg, respectively) and group 7 (vitamin-E 100 mg/kg, positive control). The doses were administered orally for 14 days; 4 h following the last dose, a single dose of CCl (4) (1.5 mg/kg) was given orally to all the groups except group 2, and after 24 h, blood and liver of each animal were obtained. Analysis of plasma and liver homogenate exhibited significant preservation of markers of antioxidant activity, total plasma antioxidant activity (TPAA), total protein (TP), superoxide dismutase (SOD), catalase (CAT), and thiobarbituric acid reactive species (TBARS), in the pretreated groups as compared to the CCl (4) group (p < 0.05). Histology of the liver also evidenced the protection of hepatocytes against CCl (4) metabolites in the pretreated groups. The results of this study indicate the IN VIVO antioxidant activity of both extracts of the plant, which may be valuable to combat diseases involving free radicals.