Hydrogen and Oxygen Isotope Fractionation Effects in Different Organ Tissues of Grapes under Drought Conditions.

A study of different grapevine tissues and organs (root, stem, leaf, fruit) water isotope fractionation models from high-quality wine grapes produced in the Helan Mountains, a key wine-producing area in northwestern China, was undertaken. Results showed that δ2H values of local groundwater sources were more negative than rivers and precipitation. Soil water δ2H and δ18O values were significantly higher than those of other environmental water sources. Water from the soil surface layer (0-30 cm, δ2H and δ18O values) was more positive than the deeper layer (30-60 cm), indicating that soil water has undergone a positive fractionation effect. δ2H and δ18O values of tissues and organs from different grape varieties followed a similar pattern but were more negative than the local atmospheric precipitation line (slope between 4.1 to 5.2). The 2H and 18O fractionation relationship in grapevine organs was similar, and 18O has a higher fractionation effect than 2H. δ2H and δ18O values showed a strong fractionation effect during the transportation of water to different grape organs (trend of stem > fruit > leaf). This study showed that 18/16O fractionation in grapes is more likely to occur under drought conditions and provides a theoretical basis to improve traceability accuracy and origin protection of wine production areas.

A smartphone-based fluorospectrophotometer and ratiometric fluorescence nanoprobe for on-site quantitation of pesticide residue.

Cost-effective and user-friendly quantitation at points-of-need plays an important role in food safety inspection, environmental monitoring, and biomedical analysis. This study reports a stand-alone smartphone-based fluorospectrophotometer (the SBS) installed with a custom-designed application (the SBS-App) for on-site quantitation of pesticide using a ratiometric sensing scheme. The SBS can collect fluorescence emission spectra in the wavelength range of 380-760 nm within 5 s. A ratiometric fluorescence probe is facilely prepared by directly mixing the blue-emissive carbon nanodots (the Fe3+-specific fluorometric indicator) and red-emissive quantum dots (the internal standard) at a ratio of 11.6 (w/w). Based on the acetylcholinesterase/choline oxidase dual enzyme-mediated cascade catalytic reactions of Fe2+/Fe3+ transformation, a ratiometric fluorescence sensing scheme is developed. The practicability of the SBS is validated by on-site quantitation of chlorpyrifos in apple and cabbage with a comparable accuracy to the GC-MS method, offering a scalable solution to establish a cost-effective surveillance system for pesticide pollution.

Towards Verifying the Imported Soybeans of China Using Stable Isotope and Elemental Analysis Coupled with Chemometrics.

Verifying the geographical origin of soybeans (Glycine max [Linn.] Merr.) is a major challenge as there is little available information regarding non-parametric statistical origin approaches for Chinese domestic and imported soybeans. Commercially procured soybean samples from China (n = 33) and soybeans imported from Brazil (n = 90), the United States of America (n = 6), and Argentina (n = 27) were collected to characterize different producing origins using stable isotopes (δ2H, δ18O, δ15N, δ13C, and δ34S), non-metallic element content (% N, % C, and % S), and 23 mineral elements. Chemometric techniques such as principal component analysis (PCA), linear discriminant analysis (LDA), and BP-artificial neural network (BP-ANN) were applied to classify each origin profile. The feasibility of stable isotopes and elemental analysis combined with chemometrics as a discrimination tool to determine the geographical origin of soybeans was evaluated, and origin traceability models were developed. A PCA model indicated that origin discriminant separation was possible between the four soybean origins. Soybean mineral element content was found to be more indicative of origin than stable isotopes or non-metallic element contents. A comparison of two chemometric discriminant models, LDA and BP-ANN, showed both achieved an overall accuracy of 100% for testing and training sets when using a combined isotope and elemental approach. Our findings elucidate the importance of a combined approach in developing a reliable origin labeling method for domestic and imported soybeans in China.

A comparative authentication study of fresh fruit and vegetable juices using whole juice and sugar-specific stable isotopes.

Not-from-concentrate (NFC) juice has better nutrition, flavor and higher price than reconstituted juice. Accordingly, NFC juice is prone to adulteration and is an ongoing industry problem that has not yet been resolved. Undeclared addition of water and sugar are the main forms of NFC juice adulteration. This paper investigates the carbon and oxygen stable isotope ratios (δ13C and δ18O values) of the bulk juice and different juice components from 21 fruit and vegetable juices, and qualitatively and quantitatively analyzes the addition of water and sugar in NFC juices. The results show that the use of fruit pulp can help to qualitatively and quantitatively indicate the presence of C4 plant sugars in NFC juice, and can reliably detect added C4 plant sugars above 7 %. Sugar-specific isotope analysis (SSIA) technology was used to determine the δ13C values of different sugars (sucrose, glucose and fructose) and carbon content to qualitatively infer C3 plant sugar addition. Pulp extracted from juice had a good linear relationship with the juice water δ18O values (R2 >0.90). The addition of water to NFC juice can also be determined by comparing δ18O values of extraneous water, pulp and filtered juice. Stable isotope technology confirmed NFC juice adulteration of in-market samples using the pulp as an internal reference and was found to be a useful tool to detect adulteration of in-market NFC juice.

Origin verification of French red wines using isotope and elemental analyses coupled with chemometrics.

Origin verification of 240 French wines from four regions of France was undertaken using isotope and elemental analyses. Our aim was to identify and differentiate the geographical origin of these red wines, and more importantly, to build a classification tool that can be used to verify geographic origin of French red wines using machine learning models. Multivariate analyses of the isotopic and elemental data revealed that it is possible to determine the geographical origin of French wines with a high level of confidence for most regions analyzed in this study. The wine verification accuracy of four French wine producing regions of Bordeaux, Burgundy, Languedoc-Roussillon and Rhone using an Artificial Neural Network (ANN) method was 98.2%. The results also show that ANN is more suitable than Discriminant Analysis for this verification purpose. The most important variables for French wine regional traceability were Mg, Mn, Na, Sr, Ti and Rb.

Verification of imported red wine origin into China using multi isotope and elemental analyses.

Multi-isotope and multi-elemental analyses were performed on 600 red wine samples imported into China from 7 different countries and compared with Chinese wine. Carbon and oxygen isotopes and 16 elements were used to determine origin traceability. Our goal was to build a classification tool using data modeling that can verify the geographic origin of wines imported into China. Multivariate analyses of the isotopic and elemental data revealed that it is possible to determine the geographical origin for most imported wines with a high level of confidence (>90%). The results show that Artificial Neural Network method had a high discrimination accuracy and is more suitable than Discrimination Analysis and Random Forest methods when it comes to classifying wine origin on a global scale. In conclusion, stable isotope and trace element analyses followed by multivariate processing of the data is a fast and efficient technique suitable for global wine traceability.

[Quick determination of fipronil and its metabolites in eggs by gas chromatography-triple quadrupole mass spectrometry].

A method was established for the simultaneous determination of fipronil and its metabolites in eggs by gas chromatography-tandem mass spectrometry coupled with QuEChERS. Fipronil and its metabolites were extracted from eggs with acetonitrile, and the solution was dehydrated with 150 mg anhydrous magnesium sulfate. The extracts were purified with 50 mg N-propyl ethylenediamine (PSA) and 50 mg C18, and a capillary column pesticide Ⅱ was used. The analytes were detected in timed selected reaction monitoring (timed-SRM) mode, and were quantified using external standard method with matrix correction standard curves. A good linearity in the range of 1.0-200 µg/L with correlation coefficients (R2)>0.999 was observed. The limits of quantification (LOQs) were between 0.5 and 1.0 µg/kg. The recoveries at three spiked levels (2.0, 5.0 and 10.0 µg/kg) were in the range of 87.8% to 111.5% with RSDs between 2.0% and 9.2% (n=3). This new method satisfied the related regulations of the European Union for the determination of fipronil and its metabolites in eggs.

Zuo Jin Wan reverses P-gp-mediated drug-resistance by inhibiting activation of the PI3K/Akt/NF-κB pathway.

BACKGROUND: Zuo-Jin-Wan (ZJW), a traditional Chinese medicine formula, has been identified to be effective against drug resistance in cancer. In the present study, we investigated the effect of ZJW on acquired oxaliplatin-resistant and the PI3K/Akt/NF-κB pathway in vitro. METHODS: We tested the dose-response relationship of ZJW on reversing drug-resistance by CCK-8 assay and flow cytometry analysis in vitro. The protein expression of P-gp, MRP-2, LRP, and ABCB1 mRNA expression level were evaluated by Western blot and quantitative RT-PCR. The activities of PI3K/Akt/NF-κB pathway were also examined with or without ZJW, including Akt, IκB, p65 and their phosphorylation expression. RESULTS: We found that ZJW significantly enhanced the sensitivity of chemotherapeutic drugs and increased oxaliplatin (L-OHP)-induced cell apoptosis in a time- and dose-dependent manner. Moreover, both ZJW and a PI3K specific inhibitor (LY294002) suppressed phosphorylation of Akt (Ser473) and NF-κB, which is necessary in the activation of the PI3K/Akt/NF-κB pathway. The effect of ZJW in reversing drug-resistance and suppressing phosphorylation of Akt (Ser473) and NF-κB were weakened after treatment with a PI3K/Akt activator in HCT116/L-OHP cells. CONCLUSIONS: Our study has provided the first direct evidence that ZJW reverses drug-resistance in human colorectal cancer by blocking the PI3K/Akt/NF-κB signaling pathway, and could be considered as a useful drug for cancer therapy.

Zuo Jin Wan, a Traditional Chinese Herbal Formula, Reverses P-gp-Mediated MDR In Vitro and In Vivo.

Zuo Jin Wan (ZJW), a typical traditional Chinese medicine (TCM) formula, has been identified to have anticancer activity in recent studies. In this study, we determined the underlying mechanism of ZJW in the reversal effect of multidrug resistance on colorectal cancer in vitro and in vivo. Our results showed that ZJW significantly enhanced the sensitivity of chemotherapeutic drugs in HCT116/L-OHP, SGC7901/DDP, and Bel/Fu MDR cells. Moreover, combination of chemotherapy with ZJW could reverse the drug resistance of HCT116/L-OHP cells, increase the sensitivity of HCT116/L-OHP cells to L-OHP, DDP, 5-Fu, and MMC in vitro, and inhibit the tumor growth in the colorectal MDR cancer xenograft model. ICP-MS results showed that ZJW could increase the concentration of chemotherapeutic drugs in HCT116/L-OHP cells in a dose-dependent manner. Furthermore, we showed that ZJW could reverse drug resistance of colorectal cancer cells by decreasing P-gp level in vitro and in vivo, which has been represented as one of the major mechanisms that contribute to the MDR phenotype. Our study has provided the first direct evidence that ZJW plays an important role in reversing multidrug resistance of human colorectal cancer and may be considered as a useful target for cancer therapy.

[Analyze the antibody level of enterovirus 71 about children cases of hand-foot-mouse disease outbreak].

OBJECTIVE: To analyze the Enterovirus 71 infectious status about probably cases of hand-foot-mouse disease (HFMD). METHODS: Collect the blood samples of HFDM children probably cases and test the IgG, IgM antibody by ELISA, analyzed the age and gender distribution. RESULTS: We collected 159 blood samples of children probably cases who are 1 to 5 years old. The average EV71 IgG positive rate is 63.5%, which of IgM is 12.0%. The positive rate of EV71 IgG is decrease by aged. Male's EV71 IgM positive rate is higher than female's significantly. CONCLUSION: The pathogen of this case of HFMD outbreak is EV71. Male's EV7l infectious and incidence are higher than female's. The result of this investigation could provide information to HFMD disease control.

Simultaneous determination of 42 organic chemicals in bottled water by combining C18 extraction disk with GC-MS and LC/MS/MS technique.

A method for the determination of 42 hazard residues required by 'Japan Positive List System' in bottled water was described. Hazard compounds in bottled water were extracted with a solid phase extraction step using C18 disks. Determination was carried out by gas chromatography/mass spectrometry (GC/MS) and liquid chromatography-tandem mass spectrometry (LC/MS/MS). The disk extraction has high throughput which is well adapted to isolate and enrich these compounds from large volumes of water. For the water sample spiked at three concentration levels (LOQ, 4 times LOQ and 8 times LOQ), the recoveries of all analytes ranged between 65% and 120% with a relative standard deviation<24% (n=8).

[Determination of flumioxazin residue in foods using gas chromatography-mass spectrometry].

A method for the determination of flumioxazin residue in foods by gas chromatography-mass spectrometry (GC-MS) has been developed. The food sample was extracted with acetonitrile or ethyl acetate, concentrated in a rotary evaporator, then dissolved in acetonitrile-methyl benzene (3 : 1, v/v) and purified with an NH2-solid phase extraction (SPE) column. The final extract was analyzed by gas chromatography-mass spectrometry with selected ion monitoring mode (GC-MS-SIM). External standard method was used for the quantification. The mean recoveries of flumioxazin spiked in foods were 79.4% - 101%, and the relative standard deviations were 0.242% -7.15% (n = 10). The detection limit for each was 0.01 mg/kg. This method has high sensitivity, veracity and is suitable for the determination of pesticide residues in foods.

[Determination of 25 organochlorine pesticides in tea by gas chromatography-mass spectrometry].

A high performance gas chromatography-mass spectrometry (GC-MS) method for the determination of 25 organochlorine pesticides in tea has been developed. The samples of tea were extracted with n-hexane-acetone (2: 1, v/v). The extract was purified by using a Florisil column with n-hexane-ethyl acetate (9: 1, v/v) as elution solvent. Chromatographic analysis was performed on a DB-35MS capillary column. Satisfactory separation and sensitivity of 25 organochlorine pesticides were obtained with the proposed method. The analytical results show the working curves for 25 organochlorine pesticides were linear in the range of 0.010 - 0.500 mg/L by GC-MS on selective ion monitoring mode. The recoveries of 25 organochlorine pesticides at spiked levels of 0.01 -0.20 mg/kg were 70.8% - 105.5%, and relative standard deviations (RSDs) were 1.6% - 12.7%. The limits of quantitation were 0.01 mg/kg except that for endosulfan I and endosulfan II that were 0.02 mg/kg.

Measurement of chemical oxygen demand (COD) in natural water samples by flow injection ozonation chemiluminescence (FI-CL) technique.

COD determination based on ozone oxidation of alpha-naphthol combined with UV radiation (UV-O3) has been studied in the present work. Utilizing the phenomenon that luminol can be oxidized by the dissolved ozone to produce luminescence, we have established a new method of utilizing aqueous chemiluminescence to determine COD. The kinetics and mechanism of the ozonation reaction of alpha-naphthol have been investigated in order to gain a better understanding of the general applicability and limitation of the technique. Real world samples were analyzed and the results show that the relative error of COD(FI-CL) measurement for water samples was < 10%. Compared with the results of the conventional potassium permanganate method, the COD values of the FI-CL method are consistently higher (0-20% relative). The higher COD values suggest that the ozone-UV system is a more effective oxidation technique.