Fast, sustainable, and simultaneous analysis of water- and fat-soluble vitamins by the two-dimensional microcarbon fiber fractionation system hyphenated with MS detection.

BACKGROUND: Vitamins are micronutrients that are required for normal growth and development of living organisms. However, due to their various chemical properties (e.g., acid-base behavior, the presence of numerous forms) and fluctuating concentration levels within complex matrices, simultaneous analysis of multi-class vitamins, including their active forms, is a challenging task. The growing nutrient shortage in foods is concerning for food consumers, manufacturers, and quality control organizations. Hence, a simple, fast, and greener approach that can simultaneously analyze multi-class vitamins is required to aid food testing and clinical laboratories in evaluating vitamin content more rapidly and accurately. RESULTS: A green and rapid analytical method based on online two-dimensional microscale carbon fiber/activated carbon fiber fractionation-mass spectrometry (2DµCFs-MS) was developed and validated for simultaneous determination of vitamins (water- and fat-soluble vitamins and some analogs) in food supplements and fortified energy drinks. Vitamins have been successfully separated into three different fractions using the minimum toxic solvent (only 0.7 mL of organic solvent) in a single run within 6 min. The limit of detection (LOD) ranges from 0.1 to 10.4 ng/mL, and the limit of quantification (LOQ) ranges from 0.39 to 34.5 ng/mL. The method also showed adequate repeatability and intermediate precision, with RSD<10 % and R2 > 0.99 for most vitamins. The analytical method was evaluated in terms of greenness, with an analytical greenness (AGREE) score of 0.68. SIGNIFICANCE: The 2DµCFs-MS system was developed to separate and detect multi-class vitamins simultaneously, which can be used as a beneficial tool to investigate vitamin content for food labeling and determining the vitamins in biological fluids and other complex samples. The developed method can tackle the challenge of simultaneous and fast routine analysis of multi-class vitamins.

Specific fractionation of ginsenosides based on activated carbon fibers and online fast screening of ginseng extract by mass spectrometry.

Ginseng is beneficial in the prevention of many diseases and provides benefits for proper growth and development owing to the presence of various useful bioactive substances of diverse chemical heterogeneity (e.g., triterpenoid saponins, polysaccharides, volatile oils, and amino acids). As a result, understanding the therapeutic advantages of ginseng requires an in-depth compositional evaluation employing a simple and rapid analytical technique. In this work, three types of surface-activated carbon fibers (ACFs) were prepared by gas-phase oxidation, strong acid treatment, and Plasma treatment to obtain CO2-ACFs, acidified-ACFs, and plasma-ACFs, respectively. Three prepared ACFs were compared in terms of their physicochemical characterization (i.e., surface roughness and functional groups). A separation system was built using a column with modified ACFs, followed by mass spectrometry detection to investigate and determine substances of different polarities. Among the three columns, CO2-ACFs showed the optimum separation effect. 13 strong polar compounds (12 amino acids and1 oligosaccharide) and 15 lesser polar compounds (ginsenosides) were separated and identified successfully within 4 min in the ginseng sample. The data obtained by CO2-ACFs-TOF-MS/MS and UHPLC-TOF-MS/MS were compared. Our approach was found to be faster (4 min vs. 36 min) and greener, requiring much less solvent (1 mL vs. 10.8 mL), and power (0.06 vs. 0.6 kWh). The developed methodology can provide a faster, eco-friendly, and more reliable tool for the high-throughput screening of complex natural matrices and the simultaneous evaluation of several compounds in diverse samples.

Broadband Silicon Nitride Power Splitter Based on Bent Directional Couplers with Low Thermal Sensitivity.

Directional couplers, as power splitters, have provided a significant contribution for light splitting and combining in silicon photonics. However, the splitting ratio of conventional directional couplers is very sensitive to wavelength, which limits the bandwidth and the transmission performance of the devices. In this work, a silicon nitride bent directional coupler with large bandwidth, large fabrication tolerance, and low thermal sensitivity is proposed and demonstrated through simulation analysis and experiments. Moreover, the fabrication process of 400 nm thick silicon nitride photonic devices is described, which are compatible with complementary metal-oxide-semiconductor technology. The 1 dB bandwidth of the bent waveguide coupler can reach 80 nm, and the thermal sensitivity is reduced by 85% compared to the silicon-based devices.

On the use of a 2D-carbon microfiber fractionation system to improve flow-injection QTOF-HRMS analysis in complex matrices: the case of Abelmoschus manihot flower extracts.

A two-dimensional microscale carbon fiber/active carbon fiber system combined with a quadrupole time of flight high-resolution mass spectrometry (2DµCFs-QTOF-HRMS) system is proposed for the rapid putative identification of polar, medium-polar and weakly polar constituents in complex matrices while strongly mitigating ionic suppression effects. The capabilities of 2DµCFs-QTOF-HRMS have been proven by analysing the composition of Abelmoschus manihot flower extracts, allowing, in a single run, the detection of 41 known substances and the presence of 6 compounds never revealed before in these samples. 2DµCFs-QTOF-HRMS has been compared with traditional HPLC-MS, showing higher versatility and a significant reduction of both analysis time (70 min to 5 min) and solvent consumption (35 mL to 1.5 mL). A comparison with the results obtained by direct flow-injection MS analyses demonstrated that 2DµCFs-QTOF-HRMS leads to a more comprehensive analysis and to improved detection sensitivity. The proposed method can be considered suitable for the rapid and comprehensive analysis of food, environmental and pharmaceutical complex samples. 2DµCFs-QTOF-HRMS can thus be considered a rapid, versatile, reliable, high-throughput and economical technique that allows for the collection of information on polar, semipolar, and weakly polar components in complex matrices.

Progress in Catalytic Pyrolysis of Oil Shale.

This paper briefly describes the research status of oil shale pyrolysis technology and the main factors affecting oil shale pyrolysis, with emphasis on four kinds of commonly used catalysts: The effects of natural minerals, metal compounds, molecular sixes, and supported catalysts on the pyrolysis of oil shale were discussed. The changes of the pyrolysis mechanism and product composition of oil shale with the addition of different catalysts were discussed. Finally, the development direction of preparation of new catalysts was discussed, in order to provide a prospect for the development and utilization of unconventional and strategic alternative energy resources around the world.

Carbon Nanofibers-Based Nanoconfined Liquid Phase Filtration for the Rapid Removal of Chlorinated Pesticides from Ginseng Extracts.

A rapid nanoconfined liquid phase filtration system (NLPF) based on solvent-confined carbon nanofibers/carbon fiber materials (CNFs/CFs) was proposed to effectively remove chlorinated pesticides from ginsenosides-containing ginseng extracts. A series of major parameters that may affect the separation performance of the CNFs-NLPF method were extensively investigated, including the water solubility of nanoconfined solvents, filtration rate, ethanol content of the ginseng extracts, and reusability of the material for repeated adsorption. The developed method showed a high removal efficiency of pesticides (85.5-97.5%), high retainment rate of ginsenosides (95.4-98.9%), and consistent reproducibility (RSD < 11.8%). Furthermore, the feasibility of the CNFs-NLPF technique to be scaled-up for industrial application was systematically explored by analyzing large-volume ginseng extract (1 L), which also verified its excellent modifiable characteristic. This filtration method exhibits promising potential as a practical tool for removing pesticide residues and other organic pollutants in food samples to assure food quality and safeguard human health.

Gas purge micro solvent extraction: A rapid and powerful tool for essential oil chromatographic fingerprints.

In this work, a new an innovative micro liquid extraction technique named "gas purge micro solvent extraction" (GP-MSE) have been tested, hyphenated with gas chromatography-mass spectrometry (GC-MS), to evaluate its capability to extract volatile fractions from vegetal samples respect to classical steam distillation extraction procedure, by comparing essential oil fingerprints from three different Atractylodes species. GP-MSE showed higher extraction capabilities and sensitivities (in particular for semi-volatile components), obtaining more structured essential oil fingerprints with high reliabilities (relative standard deviation of the peak areas between 0.34% and 5.83%), requiring at the same time smaller sample amounts and reduced extraction times. Essential oil profile data were also submitted to principal component analysis and included cosine angle in order to highlight differences among the Atractylodes species under investigation. GP-MSE can be considered an alternative, simple, fast, sensitive and environmentally friendly extraction method, with high extraction efficiencies and reproducibility toward both volatile and semi-volatile compounds.

Myristoleic acid produced by enterococci reduces obesity through brown adipose tissue activation.

OBJECTIVE: Dietary fibre has beneficial effects on energy metabolism, and the majority of studies have focused on short-chain fatty acids produced by gut microbiota. Ginseng has been reported to aid in body weight management, however, its mechanism of action is not yet clear. In this study, we focused on the potential modulating effect of ginseng on gut microbiota, aiming to identify specific strains and their metabolites, especially long-chain fatty acids (LCFA), which mediate the anti-obesity effects of ginseng. DESIGN: Db/db mice were gavaged with ginseng extract (GE) and the effects of GE on gut microbiota were evaluated using 16S rDNA-based high throughput sequencing. To confirm the candidate fatty acids, untargeted metabolomics analyses of the serum and medium samples were performed. RESULTS: We demonstrated that GE can induce Enterococcus faecalis, which can produce an unsaturated LCFA, myristoleic acid (MA). Our results indicate that E. faecalis and its metabolite MA can reduce adiposity by brown adipose tissue (BAT) activation and beige fat formation. In addition, the gene of E. faecalis encoding Acyl-CoA thioesterases (ACOTs) exhibited the biosynthetic potential to synthesise MA, as knockdown (KD) of the ACOT gene by CRISPR-dCas9 significantly reduced MA production. Furthermore, exogenous treatment with KD E. faecalis could not reproduce the beneficial effects of wild type E. faecalis, which work by augmenting the circulating MA levels. CONCLUSIONS: Our results demonstrated that the gut microbiota-LCFA-BAT axis plays an important role in host metabolism, which may provide a strategic advantage for the next generation of anti-obesity drug development.

[One-step extraction method of phthalate esters in vegetable oils].

In order to develop a fast investigation method for phthalate esters (PAEs) from vegetable oils, a gas-liquid micro-extraction (GLME) technique that combined with GC-MS was established. A vegetable oil sample (0.1 g) was directly added into the GLME device. The integrated process of extraction, clean-up, and concentration of PAEs was completed within 5 min. Internal standard method was applied to ensure the accuracy of the results. Soybean oil, blend oil, olive oil, and sesame oil were spiked with 200 µg/kg of a mixed 15 PAEs standard, and the ranges of the recoveries and RSDs were between 60.0% to 112.3% and 0.9% to 28.4%, respectively. Compared with some traditional sample pretreatment methods such as liquid-liquid extraction, liquid-liquid micro-extraction, gel permeation chromatography, this method is simple and fast, with high accuracy, good repeatability and low matrix effect. This study verified the suitability of the GLME method for field detection of food products in food safety sector and exhibits great significance for the completion of food safety system in China.

Metabolite profiling of ginsenosides in rat plasma, urine and feces by LC-MS/MS and its application to a pharmacokinetic study after oral administration of Panax ginseng extract.

Panax ginseng is widely consumed as a functional food in the form of tea, powder, capsules, among others, and possesses a range of pharmacological activities including adaptogenic, immune-modulatory, anti-tumor, anti-aging and anti-inflammatory effects. The aim of this study was to identify and quantify the major ginsenosides and their metabolites in rat plasma, urine and feces after administration of P. ginseng extract using LC-MS/MS. We collected rat plasma samples at 0.5, 1, 2, 4, 8, 12, 24 and 48 h, and the amounts of urine and fecal samples accumulated in 24 h. Fourteen major ginsenosides and their metabolites were observed in fecal samples at high levels; however, low levels of 11 ginsenosides were detected in urine samples. The pharmacokinetics of the major ginsenosides and their metabolites was investigated in plasma. The results indicated that the maximum plasma concentration, time to maximum concentration and area under the curve of compound K were significantly greater than those of other ginsenosides. This study thus provides valuable information for drug development and clinical application of P. ginseng.

Amelioration of Intestinal Barrier Dysfunction by Berberine in the Treatment of Nonalcoholic Fatty Liver Disease in Rats.

OBJECTIVE: To investigate the effect of berberine (BBR) on intestinal barrier function in nonalcoholic fat liver disease (NAFLD) in rats. MATERIALS AND METHODS: Rats were divided into three groups: normal diet group (control group [CON group]), high-fat diet feeding group (HFD group), and HFD with BBR group. After 8 weeks of HFD feeding, rats in the BBR group were given BBR intragastrically at a dose of 150 mg/kg daily for 4 weeks. The same volume of normal saline was given to the CON and HFD groups. Liver index was detected, and Sudan black B staining was used to study fatty degeneration, also the expression level of occluding and intestinal flora was analyzed. RESULTS: BBR administration significantly reduced HFD-induced increase in body weight (CON group: 379.83 ± 61.51 g, HFD group: 485.24 ± 50.15 g, and BBR group: 428.60 ± 37.37 g). It obviously alleviated the HFD-induced liver fatty degeneration and histopathological changes of intestinal mucosa according to liver index low-density lipoprotein-cholesterol, high-density lipoprotein-cholesterol, and total cholesterol (P < 0.05). The triglyceride, alanine transaminase, and aspartate aminotransferase levels were greatly elevated after BBR treatment (P < 0.05); while endotoxin, intestinal fatty acid-binding protein, and tumor necrosis factor-α were significantly reduced (P < 0.05). Moreover, we found that BBR could obviously elevate the level of occludin and decrease the level of Faecalibacterium prausnitzii and upregulate the level of bacteroides. CONCLUSION: BBR provides significant protection in NAFLD through ameliorating intestinal barrier function. SUMMARY: Berberine (BBR), an alkaloid that can be isolated from many plants, has been medically used for its wide range of antimicrobial and anti-inflammatory effectsThis is a study of BBR on liver function and intestinal barrier function in nonalcoholic fat liver disease (NAFLD)BBR treatment for NAFLD could significantly restore the liver function and provide significant protection in NAFLD through ameliorating intestinal barrier function. Abbreviations used: BBR: Berberine, NAFLD: Nonalcoholic fat liver disease, ALT: Alanine transaminase, AST: Aspartate aminotransferase, TG: Triglyceride, I-FABP: Intestinal-fatty acid-binding protein, IBD: Inflammatory bowel disease.

A high throughput mass spectrometry screening analysis based on two-dimensional carbon microfiber fractionation system.

A novel high-throughput, solvent saving and versatile integrated two-dimensional microscale carbon fiber/active carbon fiber system (2DµCFs) that allows a simply and rapid separation of compounds in low-polar, medium-polar and high-polar fractions, has been coupled with ambient ionization-mass spectrometry (ESI-Q-TOF-MS and ESI-QqQ-MS) for screening and quantitative analyses of real samples. 2DµCFs led to a substantial interference reduction and minimization of ionization suppression effects, thus increasing the sensitivity and the screening capabilities of the subsequent MS analysis. The method has been applied to the analysis of Schisandra Chinensis extracts, obtaining with a single injection a simultaneous determination of 33 compounds presenting different polarities, such as organic acids, lignans, and flavonoids in less than 7min, at low pressures and using small solvent amounts. The method was also validated using 10 model compounds, giving limit of detections (LODs) ranging from 0.3 to 30ngmL-1, satisfactory recoveries (from 75.8 to 93.2%) and reproducibilities (relative standard deviations, RSDs, from 1.40 to 8.06%).

Comparative Analysis of the Rats' Gut Microbiota Composition in Animals with Different Ginsenosides Metabolizing Activity.

Following oral intake of Panax ginseng, major ginsenosides are metabolized to deglycosylated ginsenosides by gut microbiota before absorption into the blood. As the composition of gut microbiota varies between individuals, metabolic activities are significantly different. We selected 6 rats with low efficiency metabolism (LEM) and 6 rats with high efficiency metabolism (HEM) from 60 rats following oral administration of Panax ginseng extract, and analyzed their gut microbiota composition using Illumina HiSeq sequencing of the 16S rRNA gene. The components of gut microbiota between the LEM and HEM groups were significantly different. Between the 2 groups, S24-7, Alcaligenaceae, and Erysipelotrichaceae occupied most OTUs of the HEM group, which was notably higher than the LEM group. Furthermore, we isolated Bifidobacterium animalis GM1 that could convert the ginsenoside Rb1 to Rd. The result implies that these specific intestinal bacteria may dominate the metabolism of Panax ginseng.

Determination of diamondoids in crude oils using gas purge microsyringe extraction with comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry.

Based on a homemade device, gas purge microsyringe extraction (GP-MSE) of crude oil samples was developed for the first time. As a simple, fast, low-cost, sensitive and solvent-saving technique, GP-MSE provides some outstanding advantages over the widely used sample preparation methods for crude oils such as column chromatography (ASTM D2549). Several parameters affecting extraction efficiency were optimized, including extraction temperature, extraction time, extraction solvent, condensing temperature and purge gas flow rate. With the optimized GP-MSE conditions, several real crude oil samples were extracted, and trace diamondoids were determined using comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS). In total, more than 100 diamondoids were detected and 27 marker compounds were identified and quantified accurately. The limits of detection (LODs, S/N=3) were less than 0.08µg/L for all diamondoids. The relative standard deviation (RSD) was below 8%, ranging from 1.1 to 7.6%. The linearity of the developed method was in the range of 0.5-100.0µg/L with correlation coefficients (R2) more than 0.996. The recoveries obtained at spiking 50µg/L were between 81 and 108% for diamondoids in crude oil samples. The developed method can also be extended to the analysis of other components in crude oils and other complex matrices.

Biotransformation of gypenoside XVII to compound K by a recombinant ß-glucosidase.

OBJECTIVE: To study the ß-glucosidase gene (bgy1) from Lactobacillus brevis that was cloned and expressed in Escherichia coli BL21 (DE3) and then using it for the biotransformation of gypenoside XVII. RESULTS: The bgy1 gene consists of 2283 bp encoding 761 amino acids, with homology to the glycosyl hydrolase family-3 protein domain. The enzyme (Bgy1) hydrolyzed the glucose moieties at the C-3 position and the outer glucose moieties at the C-20 position of gypenoside XVII. Using 0.1 mg enzyme ml(-1) in 20 mM sodium phosphate buffer at 30 °C and pH 6.0, 1 mg gypenoside XVII ml(-1) was transformed into 0.58 mg compound K ml(-1) within 6 h, with a corresponding molar conversion yield of 89 %. CONCLUSION: The recombinant Bgy1 is considered potentially useful for the practical preparation of compound K.

Microextraction techniques for the determination of volatile and semivolatile organic compounds from plants: a review.

Vegetables and fruits are necessary for human health, and traditional Chinese medicine that uses plant materials can cure diseases. Thus, understanding the composition of plant matrix has gained increased attention in recent years. Since plant matrix is very complex, the extraction, separation and quantitation of these chemicals are challenging. In this review we focus on the microextraction techniques used in the determination of volatile and semivolatile organic compounds (such as esters, alcohols, aldehydes, hydrocarbons, ketones, terpenes, sesquiterpene, phenols, acids, plant secondary metabolites and pesticides) from plants (e.g., fruits, vegetables, medicinal plants, tree leaves, etc.). These microextraction techniques include: solid phase microextraction (SPME), stir-bar sorptive extraction (SBSE), single drop microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), dispersive liquid liquid microextraction (DLLME), and gas purge microsyringe extraction (GP-MSE). We have taken into consideration papers published from 2008 to the end of January 2013, and provided critical and interpretative review on these techniques, and formulated future trends in microextraction for the determination of volatile and semivolatile compounds from plants.

[Determination of trace elements in traditional Chinese medicine from Changbai Mountain by ICP-MS].

The effects of different digestives for the fritillaria and atractylodes were compared. Many trace elements in the planted and wild fritillaria and atractylodes were determined by ICP-MS The results show that the RSD and recovery are better if the planted and wild fritillaria and atractylodes were digested with HNO3-H2O2. Among the many elements determined from the fritillaria and atractylodes, Cu, Zn, Fe, Mg and Mn are the dominant chemicals. The content of Fe was higher in the wild fritillaria and atractylodes than that in the planted fritillaria and atractylodes, while the contents of heavy metal Pb and Cd were lower in the wild fritillaria and atractylodes than those in the planted fritillaria and atractylodes. The wild fritillaria and atractylodes contain Co, which was not determined in the planted fritillaria and atractylodes. The experimental results showed that the detection limits were lower than 0.086 ng x g(-1) with low RSD(n = 7, 4.85%) for most metal chemicals determined, and the standard recoveries (n = 7) ranged from 96.8 to 103.4%.