Determination of 19 polyphenolic compounds in tea by ultra-high performance liquid chromatography combined with quadrupole-time of flight mass spectrometry

A rapid method was presented for the determination of 19 polyphenols in tea by ultra-high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF MS).Tea samples were extracted by 50%(V/V)ethanol,then separated by Waters Acquity BEH C18 column using a binary solvent system composed of acetonitrile and water(0.1%formic acid)by gradient elution.The analytes were determined by Q-TOF MS in TOF MS and information dependent acquisition(IDA)-MS/MS mode.The results showed that mass accuracy error of the 19 polyphenols were lower than 5.0×10^(-6),good linear relationship was got in range of 0.2–500μg/L and correlation coefficient was higher than 0.9990.The LOD was in the range of 0.002–0.100 mg/kg and the LOQ was in the range of 0.004–0.200 mg/kg.Recovery of the method was in range of 78.4%–109.2%with spike levels of 0.004–2.000 mg/kg,relative standard deviations were lower than 10%.The method was simple,rapid and accurate.It could be used for the rapid screening and quantitative analysis of 19 polyphenols in tea.

Rapid Screening of 26 Organophosphorus Pesticides in Fresh Milk by Ultra Liquid Chromatography Coupled With Quadrupole-Time of Flight Mass Spectrometry

[Objectives]A rapid screening and analysis method for 26 organophosphorus agrochemicals in fresh milk was established using ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry.[Methods]Raw milk was extracted with acetonitrile solution containing 0.2%formic acid by volume,and purified with a Dikma ProElut QuECHERS solid phase extraction cartridge.Target compounds were separated on a Waters ACQUITY UPLC HSS T3 chromatographic column(2.1 mm×50 mm,1.8μm)with methanol-water solution as a mobile phase for gradient elution,and through scanning with an electrospray ion source in positive ion mode,26 kinds of organophosphorus agrochemicals could be accurately qualitatively determined within 10 min.[Results]When using formic acid acetonitrile with a volume fraction of 0.2%,there were more types of detected compounds and a greater recovery;and using B cartridge could effectively eliminate the interference of non-polar substances such as phospholipids,achieve higher number of detected compounds than those of A and C,and well separate the 26 kinds of agrochemical residues.[Conclusions]This study provides a reference method for the rapid screening of agrochemical residues in dairy cows in the future.

Screening for Plant Toxins in Honey and Herbal Beverage by Ultrahigh-Performance Liquid Chromatography-Ion Mobility-Quadrupole Time of Flight Mass Spectrometry

The standards of plant toxins were separated by a C18 column with gradient elution with 0.1% formic acid/water (V/V) and 0.1% formic acid/acetonitrile (V/V) as mobile phase and acquired by ion mobility-quadrupole time of flight mass spectrometry (IM-QTOF MS) in positive ion mode. A database of 308 plant toxins including retention time, collision cross-section (CCS) and its fragment ions was established. Honey dissolved in water or herbal beverage was extracted by acetonitrile and purified with PSA sorbent, and then acquired by ultrahigh-performance liquid chromatography IM-QTOFMS. The acquired data were processed by comparing with the database we established to confirm the target compounds. The average recoveries for samples at two levels ranged from 60.6% - 120.1%, with relative standard deviation (n = 6) less than 25%. The limit of quantitation for plant toxins ranged from 1 - 20 μg/kg. The developed screening method was used in determination of honey, herbal beverage and honey flavored tea beverage samples. The results showed that berberine was detected in one honey with 1 μg/kg and caffeine was present in some beverages with the concentration from 200 and 5500 μg/kg. This method could meet the requirement for rapid screening of plant toxins in honey and herbal beverage. It can be used for the quality control of honey and herbal beverage in enterprises or quality inspection departments. It also can be used in the rapid screening of food poisoning.

Exact Mass Measurements for α-Allenic Alcohol by Atmospheric Pressure Chemical Ionization/Time-of-flight Mass Spectrometry

The atmospheric pressure chemical ionization/time of flight mass spectrometry (APCI/TOF MS) was applied to determine the mass of five α allenic alcohols via their protonated molecular ions using positive ion mode. Polyethylene glycol (PEG) was used as the internal reference. All results were obtained under the resolution of about 5000 FWHM (full width at the half maximum). Solvent effects were studied and the satisfied results were obtained in acetonitrile. Compared with the theoretical values, all absolute errors were less than 1.0 mmu. The effects of nozzle potential, push pulse potential, pull pulse potential, pull bias potential and acquisition rate on exact mass determination were also discussed. APCI/TOF MS is proven to be a very sensitive analytical technique and an alternative ionization mode in analyzing thermally labile compounds with relatively weak polarity, such as α allenic alcohol.

Identification of serum biomarkers for diagnosing stage Ⅰ lung adenocarcinoma by MALDI-TOF mass spectrometry

Objective To identify specific biomarkers that could improve early diagnosis of lung adenocarcinoma using matrix-assisted laser desorption/ionization (MALDI) technology. Methods Serum samples were isolated from 17 patients with stage Ⅰ lung adenocarcinoma and 17 age-and sex-matched healthy controls,and the serum proteomic profiles were obtained by matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry. Results Compared with healthy control group,two highly expressed potential biomarkers were identified with the relative molecular weights of 6 631.64 Da and 4 964.21 Da. The two best novel protein peaks were automatically chosen for the system training and the development of the constructed model. The constructed model was then used to test an independent set of masked serum samples from 15 lung adenocarcinoma patients and 22 healthy individuals. The analysis yielded a sensitivity of 93.3%,and a specificity of 95.5%. Conclusion These results suggest that MALDI-TOF-MS ProteinChip technology is a quick,convenient,and high-output analyzing method that is capable of selecting several relatively potential biomarkers from the serum of lung adenocarcinoma patients and may have a clinical value in the future,and will provide clues to identifying new serologic biomarkers of lung adenocarcinoma.

Establishment and Preliminary Application of Two dimensional Electrophoresis and Mass Spectrometry in Ovary Study

Objective To apply two-dimensional electrophoresis and mass spectrometry in the ovary proteome researchMethods Protein extractions from mouse ovaries were run in IPGphor isoelectric focus system with 11 cm and 24 cm IPG strips respectively (pH 3～10, 0.3 mm thick), then the protein spots were identified by mass spectrometry.Results The ovary protein exactions separated by two-dimensional electrophoresis have got high resolution, and identifing protein by mass spectrometry was highly efficient and facilitly. These two techniques should facilitate further investigation of female reproduction proteome research.Conclusion These two rapid high resolutions and efficient techniques have a variety of applications foreground in female reproduction proteome pattern research.

Nocardia cyriacigeorgica infection in a patient with repeated fever and CD4+T cell deficiency:A case report

BACKGROUND Nocardia pneumonia shares similar imaging and clinical features with pulmonary tuberculosis and lung neoplasms,but the treatment and anti-infective medication are completely different.Here,we report a case of pulmonary nocardiosis caused by Nocardia cyriacigeorgica(N.cyriacigeorgica),which was misdiagnosed as community-acquired pneumonia(CAP)with repeated fever.CASE SUMMARY A 55-year-old female was diagnosed with community-acquired pneumonia in the local hospital because of repeated fever and chest pain for two months.After the anti-infection treatment failed in the local hospital,the patient came to our hospital for further treatment.Enhanced computed tomography showed multiple patchy,nodular and strip-shaped high-density shadows in both lungs.A routine haematological examination was performed and showed abnormalities in CD19+B cells and CD4+T cells.Positive acid-fast bifurcating filaments and branching gram-positive rods were observed in the bronchoalveolar lavage fluid of the patient under an oil microscope,which was identified by matrix-assisted laser desorption ionization-time of flight mass spectrometry as N.cyriacigeorgica.The patient’s condition quickly improved after taking 0.96 g compound sulfamethoxazole tablets three times a day.CONCLUSION The antibiotic treatment of Nocardia pneumonia is different from that of common CAP.Attention should be given to the pathogenic examination results of patients with recurrent fever.Nocardia pneumonia is an opportunistic infection.Patients with CD4+T-cell deficiency should be aware of Nocardia infection.

Identification of the active ingredients from Guangtongxiao decoction in rat bile based on ultra-performance liquid chromatography/Synapt G2 quadrupole time-of-flight tandem mass spectrometry

OBJECTIVE:To identify the active ingredients and metabolites in rat bile after Guangtongxiao decoction(GTX)had been administered via the rectal route.METHODS:Drug-containing bile samples were collected via a catheter in the bile duct and could be used 5 h after rectal administration.The main active components and their metabolites in rat bile following rectal administration of GTX were identified and analyzed using ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry.RESULTS:Positive and negative modes were applied to analyze and identify the chemical ingredients in the bioactive fractions of GTX.Eight peaks were identified by comparison with the standard compounds:berberine hydrochloride,dehydrocorydaline,tetrahydropalmatine,corydaline,magnoflorine,magnolol,obacunone and albiflorin.Furthermore,60 metabolites were detected in rat bile based on mass-fragmentation behaviors,and 21 metabolites were reported for the first time.CONCLUSION:Our findings provide a solid basis for further pharmacologic and pharmacokinetic studies of GTX.

A depressant for marmatite flotation:Synthesis,characterisation and floatation performance

This study synthesised a zincic salt(ZS)as a depressant for marmatite-galena separation.The effect of ZS on the flotation of marmatite and galena was investigated through micro-flotation tests.88.89%of the galena was recovered and 83.39%of the marmatite was depressed with ZS dosage of 750 mg·L^(−1)at pH=4.The depression mechanism of ZS on marmatite was investigated by a variety of techniques,including adsorption measurements,Fourier transform infrared(FTIR),X-ray photoelectron spectroscopic(XPS)analysis,and time of flight secondary ion mass spectrometry(ToF-SIMS).Results of adsorption tests and FTIR reveal that ZS adsorbed on marmatite surface and impeded the subsequent adsorption of butyl xanthate(BX).The results of XPS and ToF-SIMS indicate that the ZnO_(2)^(3-)released by ZS could be chemisorbed on the marmatite surface and depress marmatite flotation.

Low-resistance ohmic contacts on InAlN/GaN heterostructures with MOCVD-regrown n+-InGaN and mask-free regrowth process

This paper studied the low-resistance ohmic contacts on InAlN/GaN with metal–organic chemical vapor deposition(MOCVD)regrowth technique.The 150-nm regrown n-InGaN exhibits a low sheet resistance of 31Ω/□,resulting in an extremely low contact resistance of 0.102Ω·mm between n^(+)-InGaN and InAlN/GaN channels.Mask-free regrowth process was also used to significantly improve the sheet resistance of InAlN/GaN with MOCVD regrown ohmic contacts.Then,the diffusion mechanism between n^(+)-InGaN and InAlN during regrowth process was investigated with electrical and structural characterizations,which could benefit the further process optimization.

新型减肥药利莫纳班的离子阱质谱和电子轰击质谱研究

Rimonabant was studied by ESI ion trap mass spectrometry and EI(electron impact) time-of-flight mass spectrometry.m/z 380.9 can be used for identification of this drug by LC-MS.An exact mass at m/z 462.0782 (calculated 462.0781) with abundance (8.56%) in the spectra was found for its molecular ion.Ten characteristic fragment peaks with relatively strong intensities were observed,which can be used for identification of this drug.

笼内金属富勒烯的合成与分析

自1985年,Smalley等人首次在飞行时间质谱仪中检测到C60以来[1],富勒烯碳原子族的研究便不断深入,最初发现的激光蒸发含稀土化合物的石墨只能得到微量的金属富勒烯,仅限于质谱检测,直到1990年,Kratschmer等人采用石墨电子弧放电首次得到宏观量的富勒烯[2],才使得富勒烯研究进入了实质性的研究阶段.……

LCT和GCT联合鉴别未知水样中N,N-二烷基氨基乙基磺酸及其类似物

N,N-dialkylaminoethane-2-sulfonic acids are environmental marker compounds of V type nerve agents,hence analysis of them is very important for verification of the chemical weapons convention(CWC).In this article,liquid chromatography-high resolution time of flight mass spectrometry coupled with accurate mass measurement were used to discriminate N,N-disopropyl aminoethane-2-sulfonic acid and a CWC non-related compound 3-(N-Morpholino)propanesulfonic acid in Water.The method was fast,simple and accurate,proving that high resolution mass spectrometry is a good technique for the analysis of unknown toxicant.

MALDI-TOF-MS法对重组人内皮抑素蛋白分子质量测定

肿瘤的生长依赖于血管的生成,新生血管不仅为肿瘤生长提供必需的营养物质,而且为肿瘤细胞扩散提供了重要的途径[1].1997年哈佛大学的O'Reilly等[2]发现了一种内源性新血管生成抑制因子内皮抑素(Endostatin),显示出特异抑制激活的血管内皮细胞增殖和肿瘤新血管生成的生物学活性,其抗肿瘤作用具有高效、低毒、无耐药性的优点.……

Metabolomic profiling for identification of metabolites and relevant pathways for taurine in hepatic stellate cells

AIM To develop a reliable and simple method to identify important biological metabolites and relevant pathways for taurine in hepatic stellate cells(HSCs), in order to provide more data for taurine therapy.METHODS All the biological samples were analyzed by using highperformance liquid chromatography-time electrospray ionization/quadrupole-time of flight mass spectrometry. Principal component analysis and partial least squares discriminant analysis were used to identify statistically different metabolites for taurine in HSCs, and metabolomic pathway analysis was used to do pathway analysis for taurine in HSCs. The chemical structure of the related metabolites and pathways was identified by comparing the m/z ratio and ion mode with the data obtained from free online databases.RESULTS A total of 32 significant differential endogenous metabolites were identified, which may be related to the mechanism of action of taurine in HSCs. Among the seven relevant pathways identified, sphingolipid metabolism pathway, glutathione metabolism pathway and thiamine metabolism pathway were found to be the most important metabolic pathways for taurine in HSCs.CONCLUSION This study showed that there were distinct changes in biological metabolites of taurine in HSCs and three differential metabolic pathways including sphingolipid pathway, glutathione pathway and thiamine metabolism pathway might be of key importance in mediating the mechanism of action of taurine in HSCs.

Lipopeptide Antibiotics Produced by the Engineered Strain Bacillus subtilis GEB3 and Detection of Its Bioactivity

MALDI-TOF-MS technology was used for identification of lipopeptide antibiotics producedby GEB3 strain, a derivative of Bacillus subtilis 168 which was transformed by lpaB3gene. The result showed GEB3 only produced lipopeptide antibiotic surfactin. The analysisby LC-MS demonstrated that GEB3 produced standard surfactin isoforms with side chainlengths of 13,14 and 15 carbon atoms. The bioactivity detection of surfactin indicatedthat the surfactin produced by GEB3 had inhibition effect on plant pathogens Rhizoctoniasolani and Pyricularia oryzae.

UPLC-QTOF-MS Analysis on Isoflavones in Douchi

Douchi is a kind of traditional Chinese fermented soybean food.Ultra-high performance liquid chromatography quadrupole-time of flight mass spectrometry(UPLC-QTOF-MS)was applied to separate and identify 12 kinds of isoflavones in Douchi within 16 min.The chromatographic separation was carried out on an ACQUITY UPLC HSS T3 column with a gradient elution program where water containing 0.1%formic acid and acetonitrile containing 0.1%formic acid were used as mobile phases.Detection by using electrospray ionization of positive ion mode was applied in the mass spectrometry.Isoflavones were identified by determining the accurate mass and referring to references in this study.

Diagnosis of Tumor-Like Polypoid Lesions of Gallbladder by Serum Proteomic Fingerprint

Objective： To search the specific serum proteins in tumor-like polypoid lesions of the gallbladder（PLG） patients. Methods： Surface enhanced laser desorption/ionization time of flight mass spectrometry （SELDI-TOF-MS） technique and WCX Magnetic Beads were used to detect the serum proteomic fingerprint of 23 patients with tumor-like PLG, 21 patients with non tumor-like PLG and 26 normal persons. Biomarker Wizard and Biomarker Patterns Software were used in combination to analyze the data. Results： In the preliminary screening, 22 representative specific proteins for tumor-like PLG were found. Seven specific proteins showed increased expression and 15 specific proteins showed decreased expression in the tumor-like PLG patients. Three specific proteins are selected for the diagnosis of the tumor-like PLG.. Conclusion： SELDI-TOF-MS technique can be used to select specific proteins for tumor-like PLG patients, which may be useful for the diagnosis of the tumor-like PLG and the differential diagnosis with the non tumor-like PLG.

Maternal peripartum bacteremia caused by intrauterine infection with Comamonas kerstersii:A case report

BACKGROUND Comamonas kerstersii(C.kerstersii)infections have considered as non-pathogenic to humans,however due to new techniques such as matrix-assisted laser desorption ionization-time of flight mass spectrometry(MALDI-TOF-MS),more cases have been identified.CASE SUMMARY This is the first report of a maternal patient with a C.kerstersii bacteremia following caesarean section.Due to the severity of the patient’s condition;high fever and rapidly progressing organ damage,the patient was transferred to the intensive care unit.C.kerstersii was detected by metagenomic next-generation sequencing testing.Based on the drug sensitivity test,appropriate antibiotic treatment was given and the patient recovered fully.CONCLUSION This case report confirms that the detection via MALDI-TOF-MS and metagenomic next-generation sequencing testing provides a reliable basis for the diagnosis of this rare bacterial infection.