Total Ion Chromatogram Research Articles

Anti-inflammatory activity of total alkaloids from Hypecoum leptocarpum hook. f. et Thoms

Background: Hypecoum leptocarpum Hook. f. et Thoms., which is used in traditional Tibetan medicine as an antipyretic, antitussive, analgesic, and anti-inflammatory agent, contains a variety of alkaloids that could be responsible for its analgesic and anti-inflammatory properties. Objective: The present study was designed to investigate the anti-inflammatory activity of the total alkaloids from H. leptocarpum (AHL) in vitro and to elucidate the chemical structure of the anti-inflammatory components in AHL. Materials and Methods: Chemical characterization was performed using liquid chromatography/quadrupole-time-of-flight mass and diode-array detector-high performance liquid chromatography. The anti-inflammatory effects of AHL were investigated by measuring the production of inflammatory cytokines using enzyme-linked immunosorbent assay and mRNA expression by real-time polymerase chain reaction in lipopolysaccharide-induced RAW 264.7 macrophages. Results: Chemical analysis of AHL revealed the presence of seven alkaloids, protopine (13.3%), cryptopine (1.5%), leptopidinine, leptocarpine, corydamine, dihydroleptopine, and oxohydrastinine. AHL significantly suppressed the production of nitric oxide (NO), interleukin-1 beta (IL-1 β), IL-6, and tumor necrosis factor-alpha (TNF-α) in LPS-induced RAW 264.7 cells. The maximum levels of suppression of NO, IL-1 β, IL-6, and TNF-α were 86.8% ± 2.2%, 70.1% ± 1.5%, 100.1% ± 2.5%, and 50.8% ± 3.6%, respectively. IC50values of suppression of cytokine production by AHL were 7.47 ± 2.81 μg/mL (NO), 0.12 ± 0.28 μg/mL (IL-1 β), 0.56 ± 0.37 μg/mL (IL-6), and 18.95 ± 5.23 μg/mL (TNF-α). AHL was also shown to downregulate mRNA expression of inducible NO synthase, IL-1 β, IL-6, and TNF-α in vitro. Conclusion: The study provides convincing evidence that AHL has strong anti-inflammatory activity. The potent activity is likely a result of synergy between the different alkaloids. Abbreviations used: The total alkaloids from H. leptocarpum: AHL; Nitric oxide: NO; Interleukin-1 beta IL-1β; Interleukin-6: IL-6; Tumor necrosis factor-alpha: TNF-α; Prostaglandin E2: PGE2; Inducible nitric oxide synthase: iNOS; Nonsteroidal anti-inflammatory drugs: NSAIDs; lipopolysaccharide: LPS; The total ion chromatograms: TIC; The liquid chromatography/quadrupole-time of flight: LC/Q-TOF; Nuclear factor-kappa B: NF-κB; Janus kinase-signal transducers and activators of transcription: JAK-STAT.

Analytical evaluation of phenolic compounds and minerals of Opuntia robusta J.C. Wendl. and Opuntia ficus-barbarica A. Berger

ABSTRACTIn this study, 19 phenolic compounds were detected using high-throughput instrument ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry (UPLC–ESI–MS/MS) in Opuntia ficus-barbarica A. Berger and Opuntia robusta J.C. Wendl. fruits. The five macro- and five micro-minerals determined in both species were analyzed using inductively coupled plasma–mass spectrometer. The phenolic compounds, mineral content, and the antioxidant capacity of the fruits of O. robusta and O. ficus-barbarica were analyzed. All phenolic compounds and minerals varied significantly between the two species. The total of phenolic compounds content was calculated as 69.237 and 66.385 mg kg−1, respectively, in O. ficus-barbarica and O. robusta. Ferulic acid was the highest quantities, 31.620 and 26.931 mg kg−1 in O. robusta and O. ficus-barbarica, in all phenolic contents, respectively. The macroelements calcium and potassium were the most abundant in both Opuntia species. The antioxidant activity of O. ficus-barbarica and O. robusta fruit samples was measured in the extracts of hexane, ethyl acetate, methanol, and water. The DPPH assay of Opuntia samples displayed a good radical scavenging inhibition, similar to butylated hydroxyanisole and butylated hydroxytoluene standards, as half maximal inhibitory concentration IC50 = 69.32 and 67.57 μg mL−1 in ethyl acetate extracts of O. ficus-barbarica and O. robusta fruits, respectively. This work presents a suitable method for the extraction, detection, and quantification of phenolic compounds by UPLC–ESI–MS/MS. MS/MS determination for multiclass determination was validated in Opuntia samples obtaining good results.Abbreviations: ABTS, 2,2′-azino-bis-3-ethylbenzthiazoline-6-sulphonic acid; AChE, acetylcholinesterase; BChE, butyrylcholinesterase; BHA, butylated hydroxyanisole; BHT, butylated hydroxytoluene; DPPH, 2,2-diphenyl-1-picrylhydrazyl; DTNB, (5,50-Dithio-bis(2-nitrobenzoic)acid; ICP/MS, inductively coupled plasma/mass spectrometer; LoD, yhe limit of detection; MRM, multiple reaction monitoring; QEs, quercetin equivalents; PEs, pyrocatechol equivalents; R2, correlation coefficients; r, Pearson’s correlation coefficient; SD, standard deviation; TIC, total ion chromatogram; UPLC–ESI–MS/MS, ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry

Model-effects on likelihood ratios for fire debris analysis

A simple method is introduced for assessing the evidentiary value of fire debris samples. The method relies on models built by random draws from a database of ignitable liquid and substrate pyrolysis samples. A stratified random draw from database records belonging to each ASTM E1618 ignitable liquid class and the substrate class is taken in proportion to a prescribed distribution. The likelihood ratios are estimated by direct calculation from a one-level Gaussian kernel density model based on the covariance structure and multivariate means resulting from each random draw. Multiple draws result in model-related variation in the calculated likelihood ratios. The method is demonstrated for 500 random draws with replacement based on three distributions. Ten-fold cross-validation is performed for each model, with subsequent testing on laboratory burn samples. The average cross-validated receiver operating characteristic areas under the curve were 0.959, 0.956 and 0.947, for the three distributions. The mean log (base 10) of the likelihood ratio (LLR) values for the laboratory test burns of gasoline on polyester carpet and carpet padding were in the range of 1.5 to −3.1 and were qualitatively consistent with the observed gasoline contributions to the total ion chromatograms for the samples. The LLR values for laboratory test burns of a petroleum distillate on polyester carpet and carpet padding, 1.7 to −3.3, were also in qualitative agreement with the observed chromatographic patterns. The calculated LLR values for laboratory burns of a set of polyester carpet and padding samples were in the range −0.9 to −6.7.

Photocatalytic degradation of lignocaine in aqueous suspension of TiO2 nanoparticles: Mechanism of degradation and mineralization

A detailed investigation on the photocatalytic degradation and mineralization of lignocaine, a local anesthetic, under UV irradiation has been carried out in this study. The dose of TiO2 was optimized initially and was found as 250mgL−1 for the degradation of 2mgL−1 concentration of lignocaine. The scavenging experiment using isopropanol and methanol revealed that the degradation is mainly controlled by hydroxyl radical. A fast disappearance of the parent compound (within 1h) and nearly 75% of mineralization (after 6hr) were observed using this method. The relatively low mineralization efficiency is due to the evolution of various transformation products during the degradation as identified by high-resolution mass spectrometry (LC-Q-TOF-MS). Ten well-separated product peaks were observed in the total ion chromatogram (TIC) for 30min irradiated sample of lignocaine. Based on the formation of these products, a degradation mechanism is proposed involving mainly hydroxylation, N-de-ethylation, and hydrogen abstraction. As part of mineralization study, the evolution of various inorganic ions was analyzed and the ammonium ion is found as the major inorganic species. A detailed mechanism is proposed for the inorganic ion release as well.

Insight into the structural features of low-rank coals using comprehensive two dimensional gas chromatography/time-of-flight mass spectrometry

Detailed characterization of organic components in low-rank coals is essential for the utilization of coals in clean, effective and value-added ways. Two kinds of low-rank coals were subjected to sequential thermal dissolution in the order of cyclohexane, acetone, and methanol to obtain six soluble portions (SPs) from the coals. Two gas chromatographic systems, gas chromatography/mass spectrometry (GC/MS) and comprehensive two dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOF MS), were applied to the characterization of the SPs. Compared to GC/MS, a routine analytical technique for complex mixtures, GC × GC/TOF MS improves the separating power, overcomes the co-elution, and reveals more structural details in complex mixtures like coals. Low-polar compounds like aliphatic hydrocarbons and arenes tended to be extracted by cyclohexane. High content of polar alcohols and phenols were identified in the SPs of methanol. Acetone could enrich nitrogen-containing organic compounds (NCOCs) due to hydrogen bond of N–H⋯O between NCOCs and acetone. Additionally, a series of low-concentration species including some isomers in the SPs were only identified by GC × GC/TOF MS. Distributions of various classes of compounds on the two-dimensional total ion chromatograms plot were discussed according to the separation mechanism of the two columns. Detailed analysis of biomarkers was also exhibited and discussed.

Antibacterial, cytotoxicity and GC-MS analysis of <i>Psidium Guajava</i> extracts

Leaves of Psidium guajava was extracted with water, ethanol and chloroform using percolation technique. The extracts were subjected to thin layer chromatography, bioactivity and toxicity studies as well as GC-MS analysis. The TLC chromatogram revealed 3, 4 and 6 bands respectively for the water, ethanolic and chloroform extracts. Contact bio-autographic assay conducted on the extracts against the tested bacteria showed that, out of the thirteen (13) fractions tested only one (1) showed activity on the test bacteria (Rf3).The fraction was active against all the tested bacteria with strong zones of inhibition against S. Paratyphi B, moderate against S. Paratyphi A and weak against S. Typhi . S. typhi showed slight sensitivity, S. paratyphi moderately sensitive, while S. paratyphi B showed strong sensitivity. Result of the brine shrimp lethality assay showed that all the extracts were toxic in the order of chloroform extracts (31.112µg/mL) more toxic, and then ethanolic extracts (39.903µg/mL) and lastly water extracts (49.534µg/mL). The GC-MS analysis was conducted on the most active fraction (Rf3).In the total ion chromatograms (TIC), constituents including fatty acids, heterocyclic compounds and esters among others were found. The major constituents successfully matched and identified were Oleic acid (Peak 6, 35.56% peak area), Palmitic acid (Peak 2, 20.26% peak area)and were all reported to be active principles. Keywords: bacteria, Bioactivity, GC-MS analysis, Psidium guajava , thin layer chromatography, toxicity

Improvement of Detection Sensitivity of Triglyceride with Methylamine Formate as Ionization Enhancer in Reversed Phase Liquid Chromatography-Electrospray Ionization Mass Spectrometry

Abstract A novel ionization enhancer, methylamine formate, was proposed for improving the detection sensitivity of triglyceride in edible oil by reversed phase liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). The commonly used isopropanol-acetonitrile-methanol-water and isopropanol-acetonitrile were selected as the mobile phase. By using a reversed phase C18 column, and taking the corn oil in isopropyl alcohol as sample solution, we compared methylamine formate with ammonium formate, as ionization enhancers, for their effect on the detection sensitivity of triglyceride by LC-ESI-MS after screening other different ionization enhancers, such as formic acid, acetic acid, ammonium formate, ammonium acetate, butyl formate, dibutylamine formate, triethylamine formate, diethylamine formate, methylamine formate, and ethylamine formate. The result indicated that, using methylamine formate in mobile phase, the mass spectral peak response and the signal to noise ratio of trilinolein component were all about 5 times higher than that using ammonium formate. The effect of the concentration of methylamine formate ionization enhancer, the flow rate of the mobile phase and the flow rate of nebulizing gas on the detection of methylamine formate was investigated. The concentration of triglyceride components in corn oil starting to form aggregates was similar in different mobile phases in the electrospray process according to measurement of the relationship between corn oil concentrations and the total ion chromatogram peak area of triglyceride. In particular, the peak area of trilinolein was linear with its concentration in the range of 7 × 10 −7 −2 × 10 −4 M with the correlation coefficient R 2 = 0.9997, but increased slower in the higher concentration range. According to the experimental data, the mechanism for improvement of detection sensitivity of methylamine formate was suggested as that the addition of methylamine mono-charged ions with hydrophobic groups had lower solvation energy, which made the enriched addition ions easily evaporation from the droplet surface, thus improving the electrospray ionization efficiency. This method provided an effective way to improve the detection sensitivity of triglyceride in edible oil by LC-ESI-MS.

Aerobic activated sludge transformation of vincristine and identification of the transformation products

This study aims to identify (bio)transformation products of vincristine, a plant alkaloid chemotherapy drug. A batch biotransformation experiment was set-up using activated sludge at two concentration levels with and without the addition of a carbon source. Sample analysis was performed on an ultra-high performance liquid chromatograph coupled to a high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometer. To identify molecular ions of vincristine transformation products and to propose molecular and chemical structures, we performed data-dependent acquisition experiments combining full-scan mass spectrometry data with product ion spectra. In addition, the use of non-commercial detection and prediction algorithms such as MZmine 2 and EAWAG-BBD Pathway Prediction System, was proven to be proficient for screening for transformation products in complex wastewater matrix total ion chromatograms. In this study eleven vincristine transformation products were detected, nine of which were tentatively identified.

Mass-spectra-based peak alignment for automatic nontargeted metabolic profiling analysis for biomarker screening in plant samples

Nontargeted metabolic profiling analysis is a difficult task in a routine investigation because hundreds of chromatographic peaks are eluted within a short time, and the time shift problem is severe across samples. To address these problems, the present work developed an automatic nontargeted metabolic profiling analysis (anTMPA) method. First, peaks from the total ion chromatogram were extracted using modified multiscale Gaussian smoothing method. Then, a novel peak alignment strategy was employed based on the mass spectra and retention times of the peaks in which the maximum mass spectral correlation coefficient path was extracted using a modified dynamic programming method. Moreover, an automatic landmark peak-searching strategy was employed for self-adapting time shift modification. Missing peaks across samples were grouped and registered into the aligned peak list table for final refinement. Finally, the aligned peaks across samples were analyzed using statistical methods to identify potential biomarkers. Mass spectral information on the screened biomarkers could be directly imported into the National Institute of Standards and Technology library to select the candidate compounds. The performance of the anTMPA method was evaluated using a complicated plant gas chromatography–mass spectrometry dataset with the aim of identifying biomarkers between the growth and maturation stages of the tested plant.

The changes of oil palm roots cell wall lipids during pathogenesis of Ganoderma boninense

One of the first physical defences of plants against fungal infection is their cell wall. Interaction between combinations of metabolism enzymes known as the “weapons” of pathogen and the host cell wall probably determines the fate of possible invasion of the pathogen in the host. The present work aims to study the biochemical changes of cell wall lipids of oil palm roots and to determine novel information on root cell wall composition during pathogenesis of Ganoderma boninense by using Gas Chromatography Mass Spectrometry. Based on Total Ion Chromatogram analysis, 67 compounds were found more abundant in the roots infected with G. boninense compared to the healthy roots (60 compounds). Interestingly, nine new compounds were identified from the cell wall lipids of roots infected with G. boninense. These includes Cyclohexane, 1,2-dimethyl-, Methyl 2-hydroxy 16-methyl-heptadecanoate, 2-Propenoic acid, methyl ester, Methyl 9-oxohexacosanoate, 5-[(3,7,11,15-Tetramethylhexadecyl)oxy]thiophene-2carboxylic acid, Ergosta-5,7,22,24(28)-tetraen-3beta-ol, 7-Hydroxy-3',4'-methylenedioxyflavan, Glycine and (S)-4'-Hydroxy-4-methoxydalbergione, this may involve as response to pathogen invasion. This paper provides an original comparative lipidomic analysis of oil palm roots cell wall lipids in plant defence during pathogenesis of G. boninense.

Establishment of a Direct-Injection Electron Ionization-Mass Spectrometry Metabolomics Method and Its Application to Lichen Profiling.

Direct-injection electron ionization-mass spectrometry (DI-EI-MS) is a multivariate analysis method useful for characterizing biological materials. We demonstrated the use of DI-EI-MS for metabolic profiling using several closely related lichen species: Cladonia krempelhuberi, C. gracilis, C. pseudogymnopoda, and C. ramulosa. The methodology involves conversion of total ion chromatograms to integrated chromatograms and assessment of reproducibility. The qualitative DI-EI-MS method was used to profile the major and/or minor constituents in extracts of lichen samples. It was possible to distinguish each lichen sample by altering the electron energy in DI-EI-MS and examining the resulting data using one-way analysis of variance. Previously undetectable peaks, which are easy to fragment could be revealed by varying the electron energy. Our results suggest that metabolic profiling using DI-EI-MS would be useful for discriminating between subgroups within the same species. This is the first study to report the use of DI-EI-MS in a metabolomics application.

Using precursor ion scan of 184 with liquid chromatography-electrospray ionization-tandem mass spectrometry for concentration normalization in cellular lipidomic studies

Cellular lipidomic studies have been favored approaches in many biomedical research areas. To provide fair comparisons of the studied cells, it is essential to perform normalization of the determined concentration before lipidomic analysis. This study proposed a cellular lipidomic normalization method by measuring the phosphatidylcholine (PC) and sphingomyelin (SM) contents in cell extracts. To provide efficient analysis of PC and SM in cell extracts, flow injection analysis-electrospray ionization-tandem mass spectrometry (FIA-ESI-MS/MS) with a precursor ion scan (PIS) of m/z 184 was used, and the parameters affecting the performance of the method were optimized. Good linearity could be observed between the cell extract dilution factor and the reciprocal of the total ion chromatogram (TIC) area in the PIS of m/z 184 within the dilution range of 1- to 16-fold (R2 = 0.998). The calibration curve could be used for concentration adjustment of the unknown concentration of a cell extract. The intraday and intermediate precisions were below 10%. The accuracy ranged from 93.0% to 105.6%. The performance of the new normalization method was evaluated using different numbers of HCT-116 cells. Sphingosine, ceramide (d18:1/18:0), SM (d18:1/18:0) and PC (16:1/18:0) were selected as the representative test lipid species, and the results showed that the peak areas of each lipid species obtained from different cell numbers were within a 20% variation after normalization. Finally, the PIS of 184 normalization method was applied to study ischemia-induced neuron injury using oxygen and glucose deprivation (OGD) on primary neuronal cultured cells. Our results showed that the PIS of 184 normalization method is an efficient and effective approach for concentration normalization in cellular lipidomic studies.

Insight into the shift and rearrangement of carbocation in Friedel-Crafts alkylation of unsaturated fatty acids revealed by GC–MS

We observed that Friedel-Crafts alkylation of unsaturated fatty acids yielded diverse products because of the shift and rearrangement of carbocation. However, these shifts and rearrangement rules of carbocation in Friedel-Crafts alkylation were unclear. For a better understanding of these rules, the product diversity of Friedel-Crafts alkylation of oleic acid with phenyl was studied by GC–MS. The product structures were identified by the characteristic m/z obtained in electron impact ionization and the relative contents of diverse isomers were calculated by the normalization method of integration areas in extracted ion and total ion chromatograms. The results suggested there were 11 isomeric compounds, 7–17- phenyl stearic acids with relative contents ranging from 2.9% to 16.4%. The inhibition factor of the shift and rearrangement of carbocation was also being investigated. The carbocation was easily quenched by oxygen-containing compounds such as ester, ether, and alcohol. Intramolecular quenching stopped the carbocation shifting and inhibited 2–6- phenyl stearic acids formation. The study contributed to the understanding of the shift and rearrangement of carbocation, diversity of produced isomers and inhibitors in Friedel-Crafts alkylation of the unsaturated fatty acids, which were helpful in preparing and manufacturing relative unsaturated fatty acids by alkylation.

Ultra-high performance liquid chromatography tandem mass-spectrometry for simple and simultaneous quantification of cannabinoids.

Cannabis is used widely in the United States, both recreationally and for medical purposes. Current methods for analysis of cannabinoids in human biological specimens rely on complex extraction process and lengthy analysis time. We established a rapid and simple assay for quantification of Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), 11-hydroxy Δ9-tetrahydrocannabinol (11-OH THC) and 11-nor-9-carboxy-Δ9-tetrahydrocannbinol (THCCOOH) in human plasma by U-HPLC-MS/MS usingΔ9-tetrahydrocannabinol-D3 (THC-D3) as the internal standard. Chromatographic separation was achieved on an Acquity BEH C18 column using a gradient comprising of water (0.1% formic acid) and methanol (0.1% formic acid) over a 6 min run-time. Analytes from 200μL plasma were extracted using acetonitrile (containing 1% formic acid and THC-D3). Mass spectrometry was performed in positive ionization mode, and total ion chromatogram was used for quantification of analytes. The assay was validated according to guidelines set forth by Food and Drug Administration of the United States. An eight-point calibration curve was fitted with quadratic regression (r2>0.99) from 1.56 to 100ngmL-1 and a lower limit of quantification (LLOQ) of 1.56ngmL-1 was achieved. Accuracy and precision calculated from six calibration curves was between 85-115% while the mean extraction recovery was >90% for all the analytes. Several plasma phospholipids eluted after the analytes thus did not interfere with the assay. Bench-top, freeze-thaw, auto-sampler and short-term stability ranged from 92.7 to 106.8% of nominal values. Application of the method was evaluated by quantification of analytes in human plasma from six subjects.

Untargeted metabolomic profiling of seminal plasma in nonobstructive azoospermia men: A noninvasive detection of spermatogenesis.

Male factor infertility is involved in almost half of all infertile couples. Lack of the ejaculated sperm owing to testicular malfunction has been reported in 6-10% of infertile men, a condition named nonobstructive azoospermia (NOA). In this study, we investigated untargeted metabolomic profiling of the seminal plasma in NOA men using gas chromatography-mass spectrometry and advance chemometrics. In this regard, the seminal plasma fluids of 11 NOA men with TESE-negative, nine NOA men with TESE-positive and 10 fertile healthy men (as a control group) were collected. Quadratic discriminate analysis (QDA) technique was implemented on total ion chromatograms (TICs) for identification of discriminatory retention times. We developed multivariate classification models using the QDA technique. Our results revealed that the developed QDA models could predict the classes of samples using their TIC data. The receiver operating characteristic curves for these models were >0.88. After recognition of discriminatory retention time's asymmetric penalized least square, evolving factor analysis, correlation optimized warping and alternating least squares strategies were applied for preprocessing and deconvolution of the overlapped chromatographic peaks. We could identify 36 discriminatory metabolites. These metabolites may be considered discriminatory biomarkers for different groups in NOA.

Seed Oil ofMorinda citrifoliaL. as a Surfactant for Deinking Flotation

Surfactants are essential in the pulp recovery process for the removal of ink on paper to be recycled. In order to create a “green” surfactant, seed oil was extracted fromMorinda citrifoliaL. by Soxhlet extraction for 4–8 h and its composition evaluated by gas chromatography-mass spectrometry (GC-MS). The total ion chromatogram (TIC) of fatty acids ofMorinda citrifoliaL. (FAMC) indicated that extraction yields the largest amount of unsaturated fatty acids (UFA), specifically C19H34O2and C21H38O2, at 6 h. All FAMC fractions were evaluated for their suitability as a surfactant for deinking flotation. FAMC isolated after 6 h of extraction yields fatty acids that are the most suitable surfactants, as the fraction consists of mostly unsaturated fatty acids that show good interactions with the structure of common ink molecules. Our results show that the performance of the FAMC taken after 6 h of extraction approaches that of a synthetic surfactant (SS). The appropriate viscous force for deinking flotation was found to be 1.5–2.0 × 10−4 mg/mm s2when the synthetic surfactant is used compared to 1.0–1.5 × 10−4 mg/mm s2for FAMC. The higher intermolecular bonding strength in the synthetic surfactant-ink particle system requires higher viscous force.

西非七国刺猬紫檀木材浸出液分析

本文以刺猬紫檀标本为样品，选取最优的木材化学成分抽提溶剂，然后以从非洲西部七个国家进口、且海关进口货物报关单均称为刺猬紫檀木材为样品，经过抽提超声处理后，采用GC-MS技术分别分析七种木材心材提取物的总粒子流图。结论表明：提取剂采用乙醇毒性最低，其得到的抽提物最多；来自马里和贝宁的刺猬紫檀其浸出液化学比例成分与其他5国的刺猬紫檀相关性较差，而来自几内亚比绍、加纳、塞拉利昂和尼日利亚的刺猬紫檀其浸出液化学成分比例非常接近，非洲七国刺猬紫檀的浸出液中含量最多的化合物为同一种化合物，可能是一种醇类物质，分子量为312，分子式为：C20H28N2O。 In order to choose the best solvent, Pterocarpus erinaceus was selected as the sample in this paper. Then, seven kinds of Pterocarpus erinaceus were treated as specimen. They were from seven different countries in western Africa, which were called Pterocarpus erinaceus on the customs import cargo declaration form. GC-MS extraction experiments were carried out by ultrasonic treatment and evaluating the total ion chromatograms. The results showed that ethanol was more suitable for low toxicity and getting more extractum. The correlation of the chemical composition ratio of specimen from Mali and Benin was poor with the other five countries. But it was closely related to the extractum of specimen from Guinea-Bissau, Ghana, Sierra Leone and Nigeria. The most abundant compound in the extractum of the seven kinds of Pterocarpus erinaceus was the same compound, which could be a kind of alcohol. The molecular weight was 312, and the molecular formula was C20H28N2O.

Evaluation of Isotopic Abundance Ratio and Structural Properties of Magnesium Gluconate After Treatment with the Energy of Consciousness Using LC-MS and NMR Spectroscopy

The current research work was aimed to investigate the impact of The Trivedi Effect® - Energy of Consciousness Healing Treatment (Biofield Energy Healing) on the structural properties and isotopic abundance ratio (PM+1/PM) of magnesium gluconate using LC-MS and NMR spectroscopy. Magnesium gluconate was divided into two parts. One part was denoted as the control, while the another part was defined as The Trivedi Effect® Treated sample, which received the Biofield Energy Healing Treatment remotely from eighteen renowned Biofield Energy Healers. The total ion chromatogram of the control sample showed two peaks at Rt of 1.81 and 2.06 min, whereas the treated sample displayed peaks at Rt of 1.79 and 2.04 min. The ESI-MS spectra of the control and the treated samples revealed the presence of the mass for magnesium gluconate ion in two forms at m/z 447 (adduct form with methanol) and 415 (protonated ion) in positive ionization mode. But, it showed the mass for the gluconate ion at m/z 195 in the negative ionization mode. The fragmentation pattern of magnesium gluconate in the treated sample was notably altered compared with the control sample. The proton and carbon signals for CH, CH2 and CO groups in the proton and carbon NMR spectra were found almost similar for the control and treated samples. The LC-MS based isotopic abundance ratio analysis indicated that the PM+1/PM (2H/1H or 13C/12C or 17O/16O or 25Mg/24Mg) in the treated magnesium gluconate ion at m/z 415 was significantly decreased by 79.24% compared with the control sample. Similarly, the isotopic abundance ratio of PM+1/PM (2H/1H or 13C/12C or 17O/16O) in the gluconate ion was decreased by 6.62% in the treated sample compared with the control sample. The treated magnesium gluconate might be beneficial in the nutraceutical and/or pharmaceutical industries for designing various forms of formulations, which could be providing better therapeutic response against various diseases such as diabetes mellitus, allergy, aging, inflammatory diseases, immunological disorders, and other chronic infections. Consequently, The Trivedi Effect® - Energy of Consciousness Healing Treated magnesium gluconate would be more helpful for understanding the enzymatic reactions as well as assist in the designing of the novel potent enzyme inhibitors by applying its kinetic isotope effects.

Characterization of global metabolic profile of Zhi-Zi-Hou-Po decoction in rat bile, urine and feces after oral administration based on a strategy combining LC-MS and chemometrics.

Identification of metabolic profile of traditional Chinese medicine in vivo is always a challenge task. Usually, screening out and identifying the exogenous compounds manually from total ion chromatograms (TICs) of biologic samples is time-consuming and strenuous. In this study, a systematic identification strategy based on LC-MS was adopted to clarify the metabolic profiling of Zhi-Zi-Hou-Po decoction (ZZHPD) in rat. Bile, urine and feces samples of rat were obtained after oral administration and then analyzed by LC-MS after proper preparation. The xenobiotics were screened out from TICs globally and rapidly by untargeted metabolomics-driven strategy (UMDS) based on the combined of XCMS online (a web-based platform to process LC-MS data), MetAlign (a software to process LC-MS data) and SIMCA-P (a software for data analysis). Most of the xenobiotics were identified by means of series product ions filtering (sPIF), which was based on the database-hit of ZZHPD (including prototype and metabolites). Then the unmatched constituents were identified tentatively and their source and metabolic pathway were clarified by using diagnostic fragment ions strategy (DFIS). As a result, a total of 83 compounds including 44 prototype compounds and 39 metabolites were rapidly identified or tentatively characterized from the biologic samples, and among them, four of which were found for the first time. Further research on the correlations of these prototype compounds and metabolites revealed that glucuronidation is the main metabolic pathways of ZZHPD in rat bile and urine, while prototype compounds were the abundant ingredients detected in rat feces.

Ultraperformance convergence chromatography-high resolution tandem mass spectrometry for lipid biomarker profiling and identification.

Lipids represent biologically ubiquitous and highly dynamic molecules in terms of abundance and structural diversity. Whereas the potential for lipids to inform on disease/injury is promising, their unique characteristics make detection and identification of lipids from biological samples analytically demanding. We report the use of ultraperformance convergence chromatography (UPC2 ), a variant of supercritical fluid chromatography, coupled to high-resolution, data-independent tandem mass spectrometry for characterization of total lipid extracts from mouse lung tissue. The UPC2 platform resulted in lipid class separation and when combined with orthogonal column chemistries yielded chromatographic separation of intra-class species based on acyl chain hydrophobicity. Moreover, the combined approach of using UPC2 with orthogonal column chemistries, accurate mass measurements, time-aligned low- and high-collision energy total ion chromatograms, and positive and negative ion mode product ion spectra correlation allowed for confident lipid identification. Of great interest was the identification of differentially expressed ceramides that were elevated 24 h post whole thorax lung irradiation. The identification of lipids that were elevated 24 h post-irradiation signifies a unique opportunity to investigate early mechanisms of action prior to the onset of clinical symptoms in the whole thorax lung irradiation mouse model.