Simultaneous Determination of Ultraviolet Absorbers and Antibacterial Agents in Textiles by Ultra-High Performance Liquid Chromatography/Orbitrap High Resolution Mass Spectrometry

This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.

Discovery of pulmonary fibrosis inhibitor targeting TGF-b RI in Polygonum cuspidatum by high resolution mass spectrometry with in silico strategy

Pulmonary fibrosis(PF)is an irreversible lung disease that is characterized by excessive scar tissue with a poor median survival rate of 2-3 years.The inhibition of transforming growth factor-β receptor type-I(TGF-β RI)by an appropriate drug may provide a promising strategy for the treatment of this disease.Polygonum cuspidatum(PC)is a well-known traditional Chinese herbal medicine which has an anti-PF effect.Accordingly,a combination of high resolution mass spectrometry with an in silico strategy was developed as a new method to search for potential chemical ingredients of PC that target the TGF-β RI.Based on this strategy,a total of 24 ingredients were identified.Then,absorption,distribution,metabolism,and excretion(ADME)-related properties were subsequently predicted to exclude compounds with potentially undesirable pharmacokinetics behaviour.Molecular docking studies on TGF-β RI were adopted to discover new PF inhibitors.Eventually,a compound that exists in PC known as resveratrol was proven to have excellent biological activity on TGF-β RI,with an IC_(50) of 2.211 μM in vitro.Furthermore,the complex formed through molecular docking was tested via molecular dynamics simulations,which revealed that resveratrol had strong interactions with residues of TGF-β RI.This study revealed that resveratrol has significant potential as a treatment for PF due to its ability to target TGF-β RI.In addition,this research demonstrated the exploration of natural products with excellent biological activities toward specific targets via high resolution mass spectrometry in combination with in silico technology is a promising strategy for the discovery of novel drugs.

Quantification of trace amounts of impurities in high purity cobalt by high resolution inductively coupled plasma mass spectrometry

A An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of 24 elements （Be, Mg, A1, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn Sb, Ba, Pt, Au, and Pb） in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCI. The matrix effects because of the presence of excess HCI and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits were 0.016-1.50 ].tg·g^-1, the recovery ratios were 92.2%-111.2%, and the RSD was less than 3.6%. The method was accurate, quick, and convenient. It was applied to the determination of trace impurities in high purity cobalt with satisfactory results.

Determination of trace elements in high purity nickel by high resolution inductively coupled plasma mass spectrometry

The contents ofMg, Al, Si, Ti, Cr, Mn, Fe, Co, Cu, Ga, As, Se, Cd, Sb, Pb and Bi in high purity nickel were determined by high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS）. The sample was dissolved in HNO3 and HCI by microwave digestion. Most of the spectral interferences could be avoided by measuring in the high resolution mode. The matrix effects because of the presence of excess HC1 and nickel were evaluated. Correction for matrix effects was made using Sc, Rh and T1 as internal standards. The optimum conditions for the determination were tested and discussed. The detection limits range from 0.012 to 1.76 ~tg/g depending on the type of elements. The applicability of the proposed method is also validated by the analysis of high purity nickel reference material （NIST SRM 671）. The relative standard deviation （RSD） is less than 3.3%. Results for determination of trace elements in high purity nickel were presented.

Quantification of Trace Amounts of Impurities in High Purity Cobalt by High Resolution Inductively Coupled Plasma Mass Spectrometry

An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pt, Au and Pb in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects due to the presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination was tested and discussed. Correction for matrix effects, Sc, Rh and Bi were used as internal standards. The detection limits is 0.003-0.57 μg/g, the recovery ratio is 92.2%-111.2%, and the RSD is less than 3.6%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity cobalt with satisfactory results.

Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry （ HR-ICP-MS ） was investigated. To overcome some poteutially problematic spectral iuterference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02μg/ g to 6 μg/ g depending on the elements. The experimental resalts for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

Determination of Trace Elements in High Purity Gold by High Resolution Inductively Coupled Plasma Mass Spectrometry

Trace elements were determined in high purity gold by high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS）. Sample were decomposed by aqua regia. To overcome some potentially problematic spectra/ interference, measurements were acquired in both medium and high resolution modes. The matrix effects due to the presence of excessive HCl and Au were evaluated. The optimum conditions for the determination was tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits range from 0.01ug/g to 0.28ug/g depending on the elements. The method is accurate, quick and convenient. It has been applied to the determination of trace elements in high purity gold with satisfactory results.

High Resolution Mass Spectrometry for the Recognition and Structural Characterization of a New Antimicrobial Compound

Identification of novel specialized metabolites or bioactive compounds represents the main objective in the research field of natural product leads and drug discovery. Mass spectrometry (MS) provides a central tool to expedite and make more efficient the discovery and isolation phases, while minimizing the waste of resources on rediscovery of known compounds. MS contributes acutely to elucidation and identification of numerous species because it allows molecular mass and structural features determination. In particular, identification of the elemental composition of a precursor ion of interest by accurate mass measurement and investigation of dissociative processes undergone by the molecule, represent a worthy methodology to access the structure assignment. The aim of this study was to discover and identify novel antibacterial drugs from microbial source in a jungle of already known compounds. The focus of this paper is on the analytical strategy that permitted the disclosure of a new compound, otherwise confused with other substances. Emphasis is placed on the interpretation of the ESI-MS/MS fragmentation pattern that combined with high resolution mass determination, allowed step by step to properly deduce the exact molecular formula of an unknown component with a molecular weight higher than 1500 Daltons.

Data Analysis for High Throughput Detection of 18 Phthalates in Textiles Based on High Resolution Mass Spectrometry

Liquid chromatography coupled to high resolution mass spectrometry(LC-HRMS)was used to establish a high throughput and sensitive method for 18 phthalic acid esters(PAEs)in textiles.The method was applied to screen PAEs in 413 textile samples and 7 434 pieces of test data were analyzed.Further discussion was conducted about specific compounds,textile materials,detected value distribution and positive rate of samples.Twenty-nine percent of samples were detected with PAEs,and no samples were detected beyond regulations.Diisobutyl phthalate(DiBP),Dibutyl phthalate(DBP)and Di-2-ethylhexyl phthalate(DEHP)were detected with high frequency,and most samples were fabrics with coating and printing.This study can be used to reflect distribution of phthalate residues in textiles on the market and provide data support for risk assessment of PAEs for textile producers and consumers.

Software-aided detection and structural characterization of cyclic peptide metabolites in biological matrix by high-resolution mass spectrometry

Compared to their linear counterparts,cyclic peptides show better biological activities,such as antibacterial,immunosuppressive,and anti-tumor activities,and pharmaceutical properties due to their conformational rigidity.However,cyclic peptides could form numerous putative metabolites from potential hydrolytic cleavages and their fragments are very difficult to interpret.These characteristics pose a great challenge when analyzing metabolites of cyclic peptides by mass spectrometry.This study was to assess and apply a software-aided analytical workflow for the detection and structural characterization of cyclic peptide metabolites.Insulin and atrial natriuretic peptide(ANP)as model cyclic peptides were incubated with trypsin/chymotrypsin and/or rat liver S9,followed by data acquisition using TripleTOF?5600.Resultant full-scan MS and MS/MS datasets were automatically processed through a combination of targeted and untargeted peak finding strategies.MS/MS spectra of predicted metabolites were interrogated against putative metabolite sequences,in light of a,b,y and internal fragment series.The resulting fragment assignments led to the confirmation and ranking of the metabolite sequences and identification of metabolic modification.As a result,29 metabolites with linear or cyclic structures were detected in the insulin incubation with the hydrolytic enzymes.Sequences of twenty insulin metabolites were further determined,which were consistent with the hydrolytic sites of these enzymes.In the same manner,multiple metabolites of insulin and ANP formed in rat liver S9 incubation were detected and structurally characterized,some of which have not been previously reported.The results demonstrated the utility of software-aided data processing tool in detection and identification of cyclic peptide metabolites.

Application of Liquid Chromatography-High Resolution Time-of-flight Mass Spectrometry in the Detection of Raw Milk and Dairy Products

Milk and dairy products are more and more popular with consumers due to their various nutrients, and their quality and safety issues have always been concerned. Therefore, the development of rapid, accurate and simple screening techniques is of great significance. Liquid chromatography-high resolution time-of-flight mass spectrometry has high-resolution and high-throughput detection functions, and has gradually begun to be applied in the detection of milk and dairy products. This paper summarized the application of milk and dairy products in liquid chromatography-high resolution time-of-flight mass spectrometry, laying a foundation for the development of new methods.

Determination of Sym-triazine Residues in Animal-derived Food by Liquid Chromatography-High Resolution Mass Spectrometry

[Objective]The research aimed to establish a liquid chromatography-high-resolution mass spectrometry for detecting residues of diclazuril,toltrazuril and its metabolites in animal-derived food.[Method]The samples were pre-treated by QuEChERS technology and detected by Exactive liquid chromatography-high resolution mass spectrometry.The liquid chromatography-high-resolution mass spectrometry for detecting the residues of diclazuril,toltrazuril,toltrazuril sulfone and toltrazuril sulfoxide in animal-derived food was established.[Result]Diclazuril,toltrazuril,toltrazuril sulfone and toltrazuril sulfoxide showed a good linear correlation in the range of 2.0-50.0μg/L（r^2〉0.99）.The average recoveries of these four compounds in bovine power at the spiked levels of 2,10 and 20μg/kg were 74.5%-90.1%,and the relative standard deviations（RSD）were 15.4%-17.5%.[Conclusion]This method was stable and reliable,and could be used to detect diclazuril,toltrazuril,toltrazuril sulfone and toltrazuril sulfoxide in animal-derived food.

基于UHPLC-Q-Exactive Orbitrap HRMS技术结合化学计量学方法的不同干燥处理杜仲叶成分分析

采用基于液质联用的非靶向代谢组学技术结合化学计量学数据自动解析软件AntDAS-LCHRMS分析了4种不同干燥处理(冻干、热泵烘干、电热烘干、晒干)杜仲叶样本中的化合物。杜仲叶样本数据由超高效液相色谱-四极杆-静电场轨道阱高分辨质谱(UHPLC-Q-Exactive Orbitrap HRMS)分别在正、负离子模式下进行采集,经AntDAS-LCHRMS软件解析,共鉴定出71种差异性化合物,经标准品验证确定40种化合物,包括环烯醚萜类、有机酸类、黄酮类、氨基酸类、核苷类、维生素类等9类物质。其中,正、负离子模式下均可识别并验证的化合物有车叶草苷、绿原酸、芦丁、异槲皮苷、车叶草苷酸、京尼平苷等25种化合物。层次聚类分析(HCA)及主成分分析(PCA)结果均显示,相同处理的杜仲叶样本各自聚成一类,不同处理的杜仲叶样本可明显区分。热图分析进一步揭示了不同干燥处理杜仲叶样本中差异性化合物的含量变化。晒干处理样本中苯丙氨酸及色氨酸等氨基酸类物质的水平较高;冻干及热泵烘干处理样本中有机酸类、环烯醚萜类、糖类等含量较高;电热烘干样本中核苷类、黄酮类物质的含量较高;黄酮类物质在冻干、热泵烘干及晒干样本中差异较小。研究结果为不同干燥处理杜仲叶的成分分析、品质评价及其开发应用提供了科学依据,也可为其他复杂药用植物体系的化学成分分析提供参考。

基于UHPLC-Q-Orbitrap/MS鉴定当归四逆颗粒化学成分

本研究运用超高效液相色谱-四极杆-静电场轨道阱质谱(UHPLC-Q-Orbitrap/MS)技术快速鉴定当归四逆颗粒的化学成分。采用SUPELCO C18色谱柱(100 mm×4.6 mm×2.7μm),以0.1%甲酸水溶液-乙腈为流动相进行梯度洗脱,正、负离子模式下采集数据。根据精确质荷比和二级质谱碎片离子信息,结合相关文献快速鉴定当归四逆颗粒的成分,并对化合物的药味来源进行归属。结果表明,在正、负离子模式下,分别从当归四逆颗粒鉴定出34、38种化合物,其中包括20种黄酮类、15种有机酸类、11种皂苷类、9种萜类、5种苯酞类、1种苯丙素类、1种醛类、1种核苷类、1种木脂素类及8种其他类化合物。本研究可为阐释当归四逆颗粒的药效物质基础提供依据。

UPLC-Q-Exactive-Orbitrap-MS法同时测定牛黄上清片中18种胆汁酸的含量

目的 建立超高效液相色谱-四极杆-静电场轨道阱高分辨质谱(UPLC-Q-Exactive-Orbitrap-MS)法同时测定牛黄上清片中牛磺胆酸、7-酮-3α,12-α-羟基胆烷酸、甘氨猪去氧胆酸、12-脱氢胆酸、甘氨胆酸、3-酮-7α,12α-二羟基-5β-胆烷酸、牛磺鹅去氧胆酸、3α-羟基-7-氧代-5β-胆烷酸、猪胆酸、牛磺脱氧胆酸钠、猪去氧胆酸、胆酸、甘氨鹅脱氧胆酸、甘氨脱氧胆酸、牛磺石胆酸钠、鹅去氧胆酸、去氧胆酸、石胆酸的含量。方法 分析采用Thermo Fisher Scientfic Bremen HYPERSIL GOLD色谱柱(2.1 mm×100 mm, 1.9μm);流动相0.1%甲酸-甲醇,梯度洗脱;体积流量0.2 mL/min;柱温40℃;加热电喷雾离子源;负离子扫描;平行反应监测模式。再进行化学模式识别。结果 18种胆汁酸在各自范围内线性关系良好(r≥0.999 5),平均加样回收率96.73%~104.07%,RSD 2.10%~4.07%。不同厂家样品中各胆汁酸在种类和含量上存在一定差异。结论 该方法灵敏可靠,专属性好,可用于牛黄上清片的质量控制。

基于UPLC-Q-Orbitrap HRMS和网络药理学及分子对接分析助眠汤治疗失眠的潜在机制

目的:基于UPLC-Q-Orbitrap HRMS和网络药理学及分子对接,阐明助眠汤治疗失眠的物质基础及潜在的作用机制。方法:采用UPLC-Q-Orbitrap HRMS技术鉴定助眠汤的化学成分。流动相:0.3%甲酸水溶液(A)-乙腈(B);梯度洗脱:0~7.1 min,8%~16.7%B;7.1~7.7 min,16.7%B;7.7~8.3 min,16.7%~17%B;8.3~9.5 min,17%~18.2%B;9.5~10.1 min,18.2%B;10.1~17.3 min,18.2%~26%B;17.3~24.5 min,26%~55%B;24.5~40 min,55%B。流速:0.3 mL·min^(-1),电喷雾离子源:ESI,正、负离子模式扫描,扫描范围:m/z 50~2200。在此基础上,选择失眠的临床表现和病因作为媒介,利用在线数据库对助眠汤的促进睡眠机制潜在药效物质基础、作用靶点和作用特征进行预测分析。从煎煮后测得的活性成分的作用特点入手,运用网络药理学探究助眠汤治疗失眠的潜在机制。结果:使用UPLC-Q-Orbitrap HRMS分析并鉴定了助眠汤中391种成分,其中有43种成分能于在线数据库中找到其作用的相关靶点。使用相关数据库检索“insomnia”“sleeplessness”关键词,找到失眠相关靶点基因28182个,通过韦恩分析,预测筛选出与助眠汤失眠作用相关靶点92个,经分析,共筛选得到37个关键靶点。助眠汤通过作用于环加氧酶1(PTGS1),环加氧酶2(PTGS2),内皮型一氧化氮合酶(NOS3),DNA拓扑异构酶2(TOP2),β2肾上腺素能受体(ADRB2)等靶点和RAS、Jak-STAT等信号通路发挥对失眠症的治疗作用。结论:助眠汤呈现了多成分、多靶点、多途径治疗失眠的作用特点。

Development of an automatic measurement system using atmospheric pressure photoionization ultrahigh-resolution mass spectrometry and application for on-line analysis of particulate matter

On-line chemical characterization of atmospheric particulate matter(PM)with soft ionization technique and ultrahigh-resolution Mass Spectrometry(UHRMS)provides molecular information of organic constituents in real time.Here we describe the development and application of an automatic measurement system that incorporates PM_(2.5)sampling,thermal desorption,atmospheric pressure photoionization,and UHRMS analysis.Molecular formulas of detected organic compounds were deducted from the accurate(±10 ppm)molecular weights obtained at a mass resolution of 100,000,allowing the identification of small organic compounds in PM_(2.5).Detection efficiencies of 28 standard compounds were determined and we found a high sensitivity and selectivity towards organic amines with limits of detection below 10 pg.As a proof of principle,PM_(2.5)samples collected off-line in winter in the urban area of Beijing were analyzed using the Ionization Module and HRMS of the system.The automatic system was then applied to conduct on-line measurements during the summer time at a time resolution of 2 hr.The detected organic compounds comprised mainly CHON and CHN compounds below 350 m/z.Pronounced seasonal variations in elemental composition were observed with shorter carbon backbones and higher O/C ratios in summer than that in winter.This result is consistent with stronger photochemical reactions and thus a higher oxidation state of organics in summer.Diurnal variation in signal intensity of each formula provides crucial information to reveal its source and formation pathway.In summary,the automatic measurement system serves as an important tool for the on-line characterization and identification of organic species in PM_(2.5).

磁性分散固相微萃取/UHPLC-Q-Orbitrap HRMS测定运动营养食品中27种氨基酸

基于磁性分散固相微萃取净化,建立了测定运动营养食品中27种氨基酸含量的超高效液相色谱-四极杆-静电场轨道阱高分辨质谱法。通过优化液相色谱条件、质谱条件和样品前处理过程,在20 min内实现了对27种目标物的测定。样品经涡旋振荡,超声提取,磁性氧化石墨烯分散固相微萃取净化,采用Thermo Accucore HILIC色谱柱分离,以0.1%甲酸水溶液(含5.0 mmol/L甲酸铵)和0.1%甲酸乙腈(含5.0 mmol/L甲酸铵)为流动相进行梯度洗脱,静电场轨道阱高分辨质谱检测,外标法定量。结果表明,27种目标化合物在一定质量浓度范围内线性良好,相关系数(r^(2))均大于0.99,方法的定量下限为0.10~0.25 mg/kg,平均回收率为70.0%~93.0%,日内相对标准偏差(RSD,n=6)为1.6%~10%,日间RSD(n=5)为1.4%~5.2%。该方法高效灵敏,准确可靠,适用于运动营养食品中27种氨基酸的测定。

基于UPLC-Q-Orbitrap-MS对铁皮石斛水提物不同极性溶剂萃取物化学成分分析

目的建立超高效液相色谱串联—四极杆—静电场轨道阱质谱技术(ultra-performance liquid chromatography-linear ion trap quadrupole-Orbitrap-mass spectrometry,UPLC-Q-Orbitrap-MS)对铁皮石斛(Dendrobium officinale Kimura&Migo)水提物石油醚、乙酸乙酯、正丁醇3种萃取组分进行定性表征的方法。方法提取铁皮石斛水提物并依次用石油醚、乙酸乙酯、正丁醇萃取,旋蒸浓缩后,得到石油醚、乙酸乙酯、正丁醇萃取组分。样品经UPLC-Q-Orbitrap-MS分析,根据元素组成、分子量、质荷比、离子碎片等确定化合物信息并推导裂解规律,通过与文献、MzCloud、MzVault、PudChem、本地数据库比对确定鉴定结果。结果在正负离子模式下共鉴定出化合物62种,包括黄酮类成分20种,联苄类成分6种,羧酸及其衍生物6种,脂肪酸及其衍生物6种,酚类成分4种,氨基酸及其衍生物3种,糖类成分2种,生物碱类、苯丙素、蒽醌、萜类化合物各1种,其他类成分3种,还检测到8种含量较高、质谱信号较强的未知成分。其中水提石油醚萃取物中鉴定出化合物7种,乙酸乙酯萃取物中鉴定出化合物36种,正丁醇萃取物中鉴定出化合物48种。通过与文献比对,62种化合物中有7种化合物为首次从铁皮石斛中提取得到。结论该方法可快速有效分析铁皮石斛中多种化学成分,可为铁皮石斛质量控制及药效物质基础研究提供参考。

UPLC-Q-Orbitrap HRMS法结合分子网络分析吴茱萸汤的化学成分

采用UPLC-Q-Orbitrap HRMS技术结合分子网络,全面快速地分析和鉴定吴茱萸汤中的化学成分。使用Waters Acquity UPLC HSS T3型色谱柱(150 mm×2.1 mm,1.8μm)进行色谱分离,离子源为HESI,在正、负离子模式下进行数据采集。随后,将质谱数据导入GNPS平台生成分子网络对化合物进行分类,再将质谱数据导入Compound Discover 3.2软件进一步对化合物进行鉴定。最终在吴茱萸汤中共鉴定出100个化合物,其中以黄酮类、生物碱类、有机酸类、萜类、糖类化合物为主,还有少量的苯丙素类、苯酚类、苷类化合物。其分析方法和结果对中药复杂体系的成分表征具有借鉴价值。