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Coping with spectral interferences when measuring water stable isotopes of vegetables 在测量蔬菜的水稳定同位素时应对光谱干扰。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-05 DOI: 10.1002/rcm.9907
Barbara Herbstritt, Lena Wengeler, Natalie Orlowski

Rationale

Laser-based analyzers are widely used in ecohydrology to analyze plant water isotopic compositions (δ18O and δ2H). The suitability of three different water extraction and isotope equilibration techniques was compared. We examined whether co-extracted volatile organic compounds (VOCs) affect laser-based isotope measurements and used the instrument's spectral parameters to post-correct for interfering VOCs.

Methods

Cryogenic vacuum extraction, vapor headspace equilibration in bags, and vapor equilibration in situ probes were used to extract liquid water or water vapor for laser-based isotope analysis (cavity ring-down spectrometry, CRDS). Isotope data were calibrated by standards for each method separately. Spectral parameters of the instrument, appropriate to identify spectral interferences with MeOH and CH4, were identified and used for post-correction. Differences between the three methods and between the origins of the vegetables were identified by statistical tests.

Results

VOCs were found in various amounts for the three different methods. They were co-extracted or co-equilibrated during the different extraction or equilibration methods. Correlation coefficients of isotope data and “CH4” (spectral parameter) were 0.99 or better; however, slopes for δ18O were similar on different instrument types but different for δ2H. Our correction approach improved results and inter-comparability of the methods considerably without knowing the chemical composition of the plant sap.

Conclusions

All three methods were sensitive enough to distinguish and resolve differences in natural abundance. Data quality was improved by the “CH4 correction” approach but could probably be optimized by a plant species–specific correction. Standardized tools for contaminant removal or post-correction applications from manufacturers, in particular for vapor-mode analysis, are still needed.

理由生态水文学中广泛使用激光分析仪来分析植物水的同位素组成(δ18O 和 δ2H)。我们比较了三种不同的水提取和同位素平衡技术的适用性。我们研究了共同萃取的挥发性有机化合物(VOC)是否会影响基于激光的同位素测量,并使用仪器的光谱参数对干扰的 VOC 进行后校正:方法:使用低温真空萃取、袋装蒸汽顶空平衡和原位蒸汽平衡探头萃取液态水或水蒸气,用于激光同位素分析(腔环向下光谱法,CRDS)。每种方法的同位素数据都分别用标准进行了校准。确定仪器的光谱参数,以识别与 MeOH 和 CH4 的光谱干扰,并用于后期校正。通过统计检验确定了三种方法之间以及蔬菜产地之间的差异:结果:在三种不同的方法中发现了不同数量的挥发性有机化合物。在不同的萃取或平衡方法中,它们被共同萃取或共同平衡。同位素数据与 "CH4"(光谱参数)的相关系数为 0.99 或更高;然而,不同类型仪器的 δ18O 斜率相似,但 δ2H 的斜率不同。在不了解植物汁液化学成分的情况下,我们的校正方法大大改善了结果和方法间的可比性:结论:所有三种方法都非常灵敏,足以区分和解决自然丰度的差异。CH4校正 "方法提高了数据质量,但针对特定植物物种的校正方法可能会优化数据质量。仍然需要制造商提供标准化的污染物去除或校正后应用工具,特别是用于蒸汽模式分析的工具。
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引用次数: 0
New type of filaments for improved accuracy of multiple sulfur isotope analyses by electron-impact gas-source mass spectrometry 通过电子撞击气源质谱仪提高多硫同位素分析精度的新型灯丝。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-05 DOI: 10.1002/rcm.9873
Pierre Cartigny, Amaury Bouyon, Hartmut Bars, Nina Albrecht, Issaku E. Kohl, Guillaume Landais, Arnaud Duverger, James Farquhar

Rationale

The analysis of the three sulfur stable isotope ratios (33S/32S, 34S/32S, 36S/32S) is routinely performed by gas-source isotope ratio mass spectrometry (IRMS) on the SF6 gaseous molecule, collecting SF5+ ions at m/z ~ 127, 128, 129 and 131. High precision and accuracy are commonly achieved owing to a lack of correction because fluorine has only one isotope and the inert nature of the SF6 molecule. The analysis of the 36S/32S ratio is, however, complicated by the low abundance of 36S (~0.015%) and the possible occurrence of trace amounts of fluorocarbon compounds leading to 12C3F5+ ions at m/z ~ 131, i.e. where 36SF5+ ions are collected.

Methods

We used gas-source high-resolution IRMS to better characterize the nature of possible interferences, and we tested novel types of filaments in order to investigate their influence on possible interferences.

Results

We confirm that the 12C3F5+ ion represents the main isobaric interference at m/z ~ 131. We also demonstrate that tungsten fluoride adducts are formed from the reaction of fluorine ions derived during fragmentation of the SF6 molecule with the hot tungsten filament. These reactions lead to the formation of e.g. WF5+, WF4+, WF3+ ions, including doubly charged ions. WF4++, in particular, leads to isobaric interference on m/z ~ 128, 129 and 131 from 180WF4++, 182WF4++ and 186 WF4++ ions, respectively. Because 180W (0.12%) is at low abundance, its influence on δ33S measurements would remain negligible, but 182W (26.5%) and 186W (28.4%) lead to scale contraction for both δ34S and δ36S.

Conclusions

Rather than correcting for these interferences, or working at high mass resolution, we suggest avoiding W isobaric interferences by using other types of filaments, with initial reports on both pure Re filaments and Y2O3-coated W filaments.

理由:分析三种硫稳定同位素比(33S/32S、34S/32S、36S/32S)的常规方法是对 SF6 气体分子进行气源同位素比质谱分析(IRMS),收集 m/z ~127、128、129 和 131 的 SF5 + 离子。由于氟只有一种同位素,无需校正,加上 SF6 分子的惰性,因此通常能达到很高的精度和准确度。然而,由于 36S 的丰度较低(约为 0.015%),而且可能存在痕量碳氟化合物,导致在 m/z ~ 131 处(即收集 36SF5 + 离子的位置)出现 12C3F5 + 离子,因此 36S/32S 比率的分析变得复杂:方法:我们使用气源高分辨率红外光谱仪来更好地描述可能存在的干扰的性质,我们还测试了新型丝线,以研究它们对可能存在的干扰的影响:结果:我们证实 12C3F5 + 离子代表了 m/z ~ 131 处的主要等压干扰。我们还证明,氟化钨加合物是由 SF6 分子破碎过程中产生的氟离子与热钨丝反应形成的。这些反应会形成 WF5 +、WF4 +、WF3 + 等离子,包括双电荷离子。WF4 ++ 尤其会导致 180WF4++、182WF4 ++ 和 186 WF4 ++ 离子分别对 m/z~128、129 和 131 产生等压干扰。由于 180W(0.12%)的丰度较低,其对δ33S 测量的影响仍然可以忽略不计,但 182W(26.5%)和 186W(28.4%)会导致δ34S 和δ36S 的尺度收缩:结论:我们建议使用其他类型的灯丝来避免 W 等压线干扰,而不是校正这些干扰,或者在高质 量分辨率下工作,我们已经初步报告了纯 Re 灯丝和 Y2O3 涂层 W 灯丝。
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引用次数: 0
Pretreatment method for oxygen stable isotope ratio analysis of the sugar-rich fraction in fruit juice via isotope ratio mass spectrometry 通过同位素比质谱法对果汁中富含糖分的部分进行氧稳定同位素比分析的预处理方法。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-03 DOI: 10.1002/rcm.9906
Ayano Watanabe, Shoichi Terada

Rationale

The oxygen stable isotope ratio (δ18O) of the sugar-rich fraction of fruit juice is important as a tracer of the geographical origin of raw material. This study sought to minimize the inter-day variation of δ18O attributable to the influence of water to accurately monitor geographical origin labeling.

Methods

Two drying devices (freeze dryer and vacuum oven) were compared. Then, two humidity levels (normal and low humidity) at which the samples were placed after drying were compared. The low-humidity environment was constructed using a glove bag and pure argon gas. δ18O was measured using thermal conversion elemental analyzer/isotope ratio mass spectrometry. Improvements were made to the measurement method based on aforementioned analyses results, and the performance of the initial and improved methods was compared.

Results

δ18O of juice dried in a vacuum oven was 3.30‰ lower than that of juice dried in a freeze dryer. Moreover, δ18O of juice samples exposed to normal humidity was 3.74‰ lower than that of samples exposed to low humidity. The combined inter-day and intra-day standard deviation was reduced from 1.20‰ in the initial method to 0.42‰ in the improved method.

Conclusions

This study describes a pretreatment method for δ18O measurement in the sugar-rich fraction of fruit juice with less inter-day variation, and it will be useful for monitoring geographical origin labeling.

理由:果汁中富含糖分部分的氧稳定同位素比值(δ18O)作为原材料地理来源的示踪剂非常重要。本研究试图最大限度地减少因水的影响而导致的 δ18O 日间变化,以准确监测地理原产地标记:方法:比较了两种干燥设备(冷冻干燥机和真空烘箱)。方法:比较了两种干燥设备(冷冻干燥机和真空烘箱),然后比较了干燥后样品放置的两种湿度(正常湿度和低湿度)。低湿度环境是用手套袋和纯氩气构建的。使用热转换元素分析仪/同位素比质谱法测量 δ18O。根据上述分析结果对测量方法进行了改进,并对初始方法和改进方法的性能进行了比较。结果:真空烘箱中干燥的果汁的δ18O 比冷冻干燥机中干燥的果汁低 3.30‰。此外,正常湿度下果汁样品的δ18O 比低湿度下果汁样品的δ18O 低 3.74‰。日间和日内的综合标准偏差从初始方法的 1.20‰降至改进方法的 0.42‰:本研究介绍了一种富含糖分的果汁中δ18O 测量的预处理方法,其日间变化较小,可用于监测地理原产地标签。
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引用次数: 0
Exploring methandienone metabolites generated via homogenized camel liver: Advancements for anti-doping applications through High Resolution-Liquid Chromatography Mass Spectrometry analysis 探索通过匀浆骆驼肝脏产生的甲地孕酮代谢物:通过高分辨率液相色谱质谱分析推进反兴奋剂应用。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-03 DOI: 10.1002/rcm.9902
Ramees Abdulla Vazhat, N. A. Mohamed Farook, Jahfar Nalakath, Praseen Ondern Komathu

Rationale

Anabolic steroids, also known as anabolic–androgenic steroids (AAS), encompass steroidal androgens such as testosterone, as well as synthetic counterparts with similar structures and effects. The misuse of AAS has increased over the years, leading to ethical and welfare concerns in sports. The World Anti-Doping Agency (WADA) and the International Federation for Equestrian Sports (FEI) have banned AAS in relevant sports. Methandienone is one of the most identified anabolic androgenic steroids in sports drug testing, Therefore, reliable detection methods are crucial for effective doping control and maintaining the integrity of the sports.

Methods

This study explores the use of homogenized camel liver for detecting methandienone metabolites in camels. The biotransformation pathways of methandienone in homogenized camel liver tissues are analyzed using Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) to identify and characterize the phase I and phase II metabolites. Chromatographic separation was achieved using a Thermo-Hypersil C18 column.

Results

The study has identified 11 methandienone metabolites (M1–M11), this includes 10 phase I and one phase II metabolite. A glucuronic acid conjugate of methandienone was observed in this study, but no sulfonic acid conjugations were found. The metabolites and their possible chemical structures, along with their fragmentation patterns are confirmed using MSMS (MS2) experiments in data-independent acquisition (DIA) mode.

Conclusions

These findings serve as a vital tool for the rapid detection of methandienone, combating its illicit use in camel racing. Comprehensive screenings covering both the parent drug and its metabolites are recommended to improve detection accuracy and ensure regulatory compliance in sports doping. Future research should explore methandienone's metabolite profile in administered camel samples.

理由:合成类固醇又称合成代谢雄性类固醇(AAS),包括类固醇雄性激素(如睾酮)以及具有类似结构和效果的合成类固醇。滥用合成类固醇的现象逐年增多,引发了体育运动中的道德和福利问题。世界反兴奋剂机构(WADA)和国际马术联合会(FEI)已禁止在相关运动中使用 AAS。因此,可靠的检测方法对于有效控制兴奋剂和维护体育运动的完整性至关重要:本研究探讨了利用匀浆骆驼肝脏检测骆驼体内甲地孕酮代谢物的方法。使用液相色谱-高分辨质谱法(LC-HRMS)分析了匀浆骆驼肝脏组织中甲地孕酮的生物转化途径,以确定第一阶段和第二阶段代谢物的特征。色谱分离采用 Thermo-Hypersil C18 色谱柱:研究发现了 11 种甲地孕酮代谢物(M1-M11),其中包括 10 种 I 期代谢物和 1 种 II 期代谢物。在这项研究中观察到了甲地孕酮的葡萄糖醛酸共轭物,但没有发现磺酸共轭物。这些代谢物及其可能的化学结构,以及它们的碎片模式都是在数据独立获取(DIA)模式下通过 MSMS(MS2)实验确认的:这些发现是快速检测甲地孕酮的重要工具,有助于打击在骆驼比赛中非法使用甲地孕酮。建议对母体药物及其代谢物进行全面筛查,以提高检测准确性,确保体育兴奋剂检测符合法规要求。未来的研究应探索甲地孕酮在骆驼样本中的代谢物特征。
{"title":"Exploring methandienone metabolites generated via homogenized camel liver: Advancements for anti-doping applications through High Resolution-Liquid Chromatography Mass Spectrometry analysis","authors":"Ramees Abdulla Vazhat,&nbsp;N. A. Mohamed Farook,&nbsp;Jahfar Nalakath,&nbsp;Praseen Ondern Komathu","doi":"10.1002/rcm.9902","DOIUrl":"10.1002/rcm.9902","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Anabolic steroids, also known as anabolic–androgenic steroids (AAS), encompass steroidal androgens such as testosterone, as well as synthetic counterparts with similar structures and effects. The misuse of AAS has increased over the years, leading to ethical and welfare concerns in sports. The World Anti-Doping Agency (WADA) and the International Federation for Equestrian Sports (FEI) have banned AAS in relevant sports. Methandienone is one of the most identified anabolic androgenic steroids in sports drug testing, Therefore, reliable detection methods are crucial for effective doping control and maintaining the integrity of the sports.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>This study explores the use of homogenized camel liver for detecting methandienone metabolites in camels. The biotransformation pathways of methandienone in homogenized camel liver tissues are analyzed using Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) to identify and characterize the phase I and phase II metabolites. Chromatographic separation was achieved using a Thermo-Hypersil C18 column.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The study has identified 11 methandienone metabolites (M1–M11), this includes 10 phase I and one phase II metabolite. A glucuronic acid conjugate of methandienone was observed in this study, but no sulfonic acid conjugations were found. The metabolites and their possible chemical structures, along with their fragmentation patterns are confirmed using MSMS (MS2) experiments in data-independent acquisition (DIA) mode.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>These findings serve as a vital tool for the rapid detection of methandienone, combating its illicit use in camel racing. Comprehensive screenings covering both the parent drug and its metabolites are recommended to improve detection accuracy and ensure regulatory compliance in sports doping. Future research should explore methandienone's metabolite profile in administered camel samples.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 22","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142124304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Qualitative and quantitative characterization of elastin-like polypeptides combining low-PH/low-temperature bottom-up and intact protein liquid chromatography mass spectrometric analysis 结合低压/低温自下而上分析法和完整蛋白质液相色谱质谱分析法,对弹性蛋白样多肽进行定性和定量表征。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-02 DOI: 10.1002/rcm.9905
André Vente, Marija Mladic, Olaf Schouten, Jens Thies, Rob van der Hoeven

Rationale

Elastin-like polypeptides (ELPs) are elastic and thermoresponsive biopolymers composed of VPGXG repeats (X can be any amino acid except proline), used in biomedical applications, for example, tissue engineering and drug delivery. As different variants of ELP are mostly produced fermentatively, there is a need for the development of analysis methods that allow for absolute protein quantification in both complex matrices and purified samples and MW determination of the final products.

Methods

ELPs were intracellularly expressed in Escherichia coli quantified after cell lysis and enzymatic digestion using a proline-specific protease ProAlanase (Promega) at acidic conditions. Resulting peptides were separated by liquid chromatography, and mass spectrometry analysis was conducted by electrospray ionization high-resolution mass spectrometry using an Orbitrap mass spectrometer. The addition of a stable isotopically labeled internal standard enabled quantification in complex matrices. Prior to intact mass analysis, ELPs were purified from fermentation broth by inverse temperature cycling. Intact protein analysis was performed using reversed-phase liquid chromatography, and mass spectrometry analysis was conducted by electrospray ionization high-resolution mass spectrometry using a time-of-flight mass spectrometer.

Results

Absolute quantification of ELPs was achieved by utilizing ELP-specific properties, that is, proline-rich, soluble at low pH and low temperature. The repetitive nature of ELPs allows for sensitivity increase and use of higher dilution factors to minimize the matrix effects. Despite the lack of amino acids with charged side chains (Arg, His, Lys, Asp, and Glu) in ELP, we demonstrated successful intact protein analysis using reversed-phase LC coupled to electrospray ionization TOF MS. Moreover, truncated protein forms could be chromatographically separated and characterized as well as N-terminal modifications.

Conclusions

Both methods combined enabled quantitative and qualitative characterization of fermentatively produced ELPs.

理论依据:弹性蛋白样多肽(ELPs)是由 VPGXG 重复序列(X 可以是除脯氨酸以外的任何氨基酸)组成的具有弹性和热塌缩性的生物聚合物,可用于组织工程和药物输送等生物医学应用领域。由于 ELP 的不同变体大多通过发酵产生,因此需要开发分析方法,以便对复杂基质和纯化样品中的蛋白质进行绝对定量,并对最终产品进行分子量测定:方法:在酸性条件下,使用脯氨酸特异性蛋白酶 ProAlanase(Promega 公司)对细胞进行裂解和酶解后,在大肠杆菌中对细胞内表达的 ELPs 进行定量。用液相色谱法分离得到的肽,并使用 Orbitrap 质谱仪进行电喷雾电离高分辨质谱分析。加入稳定的同位素标记内标,可对复杂基质进行定量分析。在进行完整质量分析之前,先通过反向温度循环从发酵液中纯化 ELPs。使用反相液相色谱法进行完整蛋白质分析,并使用飞行时间质谱仪通过电喷雾离子化高分辨率质谱进行质谱分析:结果:利用ELP的特异性,即富含脯氨酸、可溶于低pH值和低温,实现了ELP的绝对定量。ELPs 的重复性使灵敏度得以提高,并可使用较高的稀释因子将基质效应降至最低。尽管 ELP 中缺乏带电侧链的氨基酸(Arg、His、Lys、Asp 和 Glu),但我们还是利用反相液相色谱结合电喷雾电离 TOF MS 成功地分析了完整的蛋白质。此外,我们还利用色谱法分离和鉴定了截短蛋白形式以及 N 端修饰:结论:这两种方法结合使用可对发酵产生的 ELP 进行定量和定性表征。
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引用次数: 0
Modern plants and sulfur isoscapes — A review, discussion, and construction of a pilot δ34S isoscape for mobility and provenance studies 现代植物与硫等值线--综述、讨论和构建用于流动性和来源研究的试验性 δ34S 等值线。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-02 DOI: 10.1002/rcm.9908
Damon Tarrant, Michael P. Richards

RATIONALE

Sulfur isotopes are increasingly used as mobility indicators in humans and animals in biology, archaeology, and forensics. However, there has been a lack of modern sulfur isotope baseline “isoscape” studies using modern plants and animals, largely due to the possibility of contamination of the S isotope values by modern pollution.

METHODS

We collected plants from across a 900-km east–west transect of British Columbia Canada and measured their sulfur isotope values. We then used a random forest model to determine which variables best explained the isotope data patterning and produced a sulfur isoscape for the southern region of British Columbia.

RESULTS

We see clear patterning in the plant sulfur isotope values that relate to geographical location and rainfall. Our model also shows that for this study area, it is unlikely that there is a significant influence of anthropogenic pollution on plant δ34S values. We also discuss the use of plants as a substrate for sulfur isoscapes and possible explanations for the often-observed difference between plant and animal δ34S values from the same region, related to differing sources of sulfur in plants compared to amino acids in human and animal tissues.

CONCLUSIONS

We found that for areas of the world where sulfur pollution is likely less widespread, it is possible to produce a modern plant S isoscape that should be an accurate baseline for mobility studies. Using random forest modelling, we have produced a baseline sulfur isoscape map of southern British Columbia that can be used for ecology, forensic and archaeological studies.

理由:在生物学、考古学和法医学中,硫同位素越来越多地被用作人类和动物的移动性指标。然而,利用现代植物和动物进行的现代硫同位素基线 "isoscape "研究一直很缺乏,这主要是由于现代污染可能会污染硫同位素值:我们收集了加拿大不列颠哥伦比亚省东西横断面长达 900 公里的植物,并测量了它们的硫同位素值。然后,我们使用随机森林模型确定哪些变量最能解释同位素数据的模式,并绘制了不列颠哥伦比亚省南部地区的硫等值线图:结果:我们发现植物硫同位素值与地理位置和降雨量有明显的相关性。我们的模型还显示,在这一研究区域,人为污染不太可能对植物的 δ34S 值产生重大影响。我们还讨论了植物作为硫等离子体基质的用途,以及同一地区植物和动物δ34S 值之间经常出现差异的可能原因,这与植物中的硫来源不同于人类和动物组织中的氨基酸有关:我们发现,在世界上硫污染可能不太普遍的地区,有可能产生现代植物 S 等值线,这应该是流动性研究的准确基线。通过随机森林建模,我们绘制了不列颠哥伦比亚省南部的硫等值线图,可用于生态学、法医学和考古学研究。
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引用次数: 0
Optimized liquid chromatography–tandem mass spectrometry protocol for enhanced detection of 45 pesticides in water and soil samples 优化液相色谱-串联质谱方案,增强对水和土壤样品中 45 种农药的检测。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-09-02 DOI: 10.1002/rcm.9904
Lingchen Meng, Wenrui Yao, Ling Wen, Xiaoli Fu, Yulin Qi, Dietrich A. Volmer

Rationale

The development of analytical screening techniques for pesticides is crucial for preventing and mitigating environmental contamination. Mass spectrometry-based screening methods differ based on the complexity of the sample matrix and the diversity of the target compounds. One of the major challenges is balancing cost reduction in the extraction process with the optimization of analytical results. This protocol introduces a universal and efficient scheme for the qualitative and quantitative schemes for 45 pesticides within a single analytical run.

Methods

Water samples were extracted using an SPE column, with the pH adjusted to 7. Soil samples were processed using a modified QuEChERS method. The pretreatment for water samples emphasized selecting appropriate SPE columns and optimizing pH, while for soil samples, the focus was on choosing suitable extraction solvents and extraction salt packages. The enriched samples were then analyzed using liquid chromatography–tandem mass spectrometry (LC–MS/MS). The method was evaluated for accuracy, precision, detection limits, and matrix effects.

Results

The method enabled the simultaneous detection of 45 pesticides within a 15-minute analysis period. SPE recoveries ranged from 56.1% to 118.8%. Instrumental detection limits varied between 0.02 and 1 pg, while method detection limits extended from 0.05 to 18.47 ng/l in soil and water matrices. The approach was successfully applied to water and soil samples, with the pesticide concentration ranging from 0.1 ng/L to 38 μg/L.

Conclusions

The protocol substantially enhances the characterization and quantification of 45 pesticides in environmental samples, achieving a remarkable reduction in detection limits by an order of magnitude compared to previous research. This method enables the simultaneous detection of pesticides in both water and soil matrices using a single system, addressing the challenges of using separate systems for different environmental media. Furthermore, this protocol provides a crucial theoretical foundation for managing and safeguarding against pesticide pollution.

理由:开发农药分析筛选技术对于预防和减轻环境污染至关重要。基于质谱的筛选方法因样品基质的复杂性和目标化合物的多样性而各不相同。主要挑战之一是如何在降低提取过程成本与优化分析结果之间取得平衡。本方案介绍了一种通用、高效的方案,可在一次分析运行中对 45 种农药进行定性和定量分析:水样采用 SPE 柱提取,pH 值调至 7。水样的预处理重点是选择合适的固相萃取柱和优化 pH 值,而土壤样品的预处理重点是选择合适的萃取溶剂和萃取盐包。然后使用液相色谱-串联质谱法(LC-MS/MS)对富集的样品进行分析。对该方法的准确度、精密度、检测限和基质效应进行了评估:结果:该方法可在 15 分钟的分析时间内同时检测 45 种农药。SPE 回收率为 56.1% 至 118.8%。在土壤和水基质中,仪器检测限在 0.02 至 1 pg 之间,方法检测限在 0.05 至 18.47 ng/l 之间。该方法成功应用于水和土壤样品,农药浓度范围为 0.1 ng/L 至 38 μg/L:该方法大大提高了环境样本中 45 种农药的定性和定量能力,与之前的研究相比,检测限显著降低了一个数量级。该方法可使用单一系统同时检测水和土壤基质中的农药,解决了针对不同环境介质使用不同系统的难题。此外,该方案还为管理和防范农药污染提供了重要的理论基础。
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引用次数: 0
Investigation of the laser fluence and wavelength dependence in surface-assisted laser desorption/ionization mass spectrometry using gold nanoparticles. 利用金纳米粒子研究表面辅助激光解吸电离质谱法中的激光通量和波长依赖性。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-08-31 DOI: 10.1002/rcm.9895
Wendy H Müller, Alexander Potthoff, Klaus Dreisewerd, Jens Soltwisch

Rationale: Surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) builds on the use of nanostructured surfaces (e.g., coatings of colloidal nanoparticles) to promote analyte desorption and ionization. The SALDI process is believed to occur mainly through thermal processes, resulting from heating of the nanosubstrate upon absorption of the photon energy, and by assisting ionization steps. Mostly due to the accessibility of the respective hardware, the majority of SALDI-MS studies use standard laser wavelengths for MALDI (i.e., 337 or 355 nm), even though peak absorption of the SALDI nanosubstrate might completely differ from these values.

Methods: Here, we investigated the wavelength dependence in SALDI-MS to determine if wavelength adjustment would be beneficial, and to provide new experimental data for a better understanding of the SALDI mechanism. To this end, gold nanoparticles (AuNPs) sprayed onto microscope glass slides were employed as SALDI nanosubstrates and L-arginine as a model analyte. In addition, we used 2,5-dihydroxyacetophenone (2,5-DHAP) for classical MALDI-MS using the same experimental setup. Arginine ion signals were recorded as a function of laser wavelength and laser fluence. Mass spectra were acquired in the wavelength range between 310 and 630 nm, including the absorption maximum of the sprayed AuNPs around 550 nm and that of 2,5-DHAP around 380 nm.

Results: Laser fluence thresholds for the generation of arginine ions were found to be dependent on the laser wavelength and to inversely correlate with the absorbance profiles of the deposited AuNPs and 2,5-DHAP, respectively. Very differently to MALDI, in SALDI ionization efficiency was found to strictly linearly decrease with increasing laser wavelength.

Conclusions: Our results, therefore, corroborate the general assumption that material ejection in SALDI-MS is mainly driven by thermal processes in the low laser fluence range and add new evidence that the ionization process is directly influenced by photon energy when AuNPs are employed as nanosubstrates.

原理:表面辅助激光解吸/电离(SALDI)质谱(MS)是利用纳米结构表面(如胶体纳米粒子涂层)来促进分析物的解吸和电离。据信,SALDI 过程主要是通过热过程(纳米基底吸收光子能量后受热)和辅助电离步骤实现的。方法:在此,我们研究了 SALDI-MS 的波长依赖性,以确定调整波长是否有益,并为更好地理解 SALDI 机制提供新的实验数据。为此,我们采用喷涂在显微镜玻璃载玻片上的金纳米粒子(AuNPs)作为 SALDI 纳米基底,并以 L-精氨酸作为模型分析物。此外,我们还使用相同的实验装置,将 2,5-二羟基苯乙酮(2,5-DHAP)用于经典的 MALDI-MS。精氨酸离子信号记录为激光波长和激光能量的函数。质谱采集的波长范围为 310 至 630 nm,其中包括喷涂 AuNPs 在 550 nm 附近的吸收最大值和 2,5-DHAP 在 380 nm 附近的吸收最大值:结果:发现生成精氨酸离子的激光通量阈值取决于激光波长,并分别与沉积的 AuNPs 和 2,5-DHAP 的吸光度曲线成反比。与 MALDI 非常不同的是,SALDI 电离效率随着激光波长的增加呈严格的线性下降趋势:因此,我们的研究结果证实了 SALDI-MS 中的物质喷射主要由低激光通量范围内的热过程驱动的一般假设,并为采用 AuNPs 作为纳米基质时离子化过程直接受光子能量影响提供了新的证据。
{"title":"Investigation of the laser fluence and wavelength dependence in surface-assisted laser desorption/ionization mass spectrometry using gold nanoparticles.","authors":"Wendy H Müller, Alexander Potthoff, Klaus Dreisewerd, Jens Soltwisch","doi":"10.1002/rcm.9895","DOIUrl":"https://doi.org/10.1002/rcm.9895","url":null,"abstract":"<p><strong>Rationale: </strong>Surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) builds on the use of nanostructured surfaces (e.g., coatings of colloidal nanoparticles) to promote analyte desorption and ionization. The SALDI process is believed to occur mainly through thermal processes, resulting from heating of the nanosubstrate upon absorption of the photon energy, and by assisting ionization steps. Mostly due to the accessibility of the respective hardware, the majority of SALDI-MS studies use standard laser wavelengths for MALDI (i.e., 337 or 355 nm), even though peak absorption of the SALDI nanosubstrate might completely differ from these values.</p><p><strong>Methods: </strong>Here, we investigated the wavelength dependence in SALDI-MS to determine if wavelength adjustment would be beneficial, and to provide new experimental data for a better understanding of the SALDI mechanism. To this end, gold nanoparticles (AuNPs) sprayed onto microscope glass slides were employed as SALDI nanosubstrates and L-arginine as a model analyte. In addition, we used 2,5-dihydroxyacetophenone (2,5-DHAP) for classical MALDI-MS using the same experimental setup. Arginine ion signals were recorded as a function of laser wavelength and laser fluence. Mass spectra were acquired in the wavelength range between 310 and 630 nm, including the absorption maximum of the sprayed AuNPs around 550 nm and that of 2,5-DHAP around 380 nm.</p><p><strong>Results: </strong>Laser fluence thresholds for the generation of arginine ions were found to be dependent on the laser wavelength and to inversely correlate with the absorbance profiles of the deposited AuNPs and 2,5-DHAP, respectively. Very differently to MALDI, in SALDI ionization efficiency was found to strictly linearly decrease with increasing laser wavelength.</p><p><strong>Conclusions: </strong>Our results, therefore, corroborate the general assumption that material ejection in SALDI-MS is mainly driven by thermal processes in the low laser fluence range and add new evidence that the ionization process is directly influenced by photon energy when AuNPs are employed as nanosubstrates.</p>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":" ","pages":"e9895"},"PeriodicalIF":1.8,"publicationDate":"2024-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Integration of high-resolution mass spectrometry technology with molecular network analysis and systems biology techniques to elucidate the active ingredients and mechanisms of Shiduqing capsules 将高分辨率质谱技术与分子网络分析和系统生物学技术相结合,阐明十渡青胶囊的有效成分和作用机制。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-08-28 DOI: 10.1002/rcm.9903
Zhiyan Liu, Shuang Li, Lei Wang, Wei Zhang, Yuanyuan Cao, Chun Bao, Chenning Zhang

Rationale

Shiduqing Capsules, a well-known Chinese patent medicine, are widely used clinically for the treatment of pruritus. However, to date, there is a lack of research on its pharmacological substances and mechanisms of action.

Methods

In the current study, the chemical components of Shiduqing Capsules were identified using UHPLC-QE-Orbitrap-MS technology. Molecular network analysis was employed to identify structurally similar compounds to the known chemical components. The potential molecular targets of the active ingredients were predicted using the SwissTargetPrediction website. The identified targets were further analyzed using gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis through the DAVID database. Molecular docking was used to validate the network pharmacology results.

Results

Ultimately, A total of 51 chemical components of Shiduqing Capsules were identified. Molecular network analysis identified 21 flavonoids and 13 terpenoids. The core targets of these ingredients include TP53, AKT1, and STAT3. GO and KEGG enrichment analysis revealed 1,371 different biological functions and 177 signaling pathways. Molecular docking confirmed the high affinity between multiple core active ingredients of Shiduqing Capsules and pruritus targets.

Conclusion

In conclusion, the effective ingredients of Shiduqing Capsules exert a multifaceted therapeutic effect on pruritus through multiple targets and pathways.

理论依据:十滴清胶囊是一种著名的中成药,临床上广泛用于治疗皮肤瘙痒症。然而,迄今为止,有关其药理物质和作用机制的研究尚属空白:本研究采用超高效液相色谱-质谱-轨道阱质谱(UHPLC-QE-Orbitrap-MS)技术对十渡青胶囊的化学成分进行了鉴定。通过分子网络分析,确定了与已知化学成分结构相似的化合物。利用 SwissTargetPrediction 网站预测了活性成分的潜在分子靶点。通过 DAVID 数据库,使用基因本体(GO)和京都基因和基因组百科全书(KEGG)通路富集分析法对确定的靶点进行了进一步分析。分子对接用于验证网络药理学结果:结果:最终确定了十渡青胶囊中的 51 种化学成分。分子网络分析确定了 21 种黄酮类化合物和 13 种萜类化合物。这些成分的核心靶点包括 TP53、AKT1 和 STAT3。GO 和 KEGG 富集分析发现了 1,371 种不同的生物功能和 177 种信号通路。分子对接证实,十渡青胶囊的多种核心活性成分与瘙痒症靶点之间具有很高的亲和力:总之,十渡青胶囊的有效成分通过多靶点、多途径对瘙痒症发挥了多方面的治疗作用。
{"title":"Integration of high-resolution mass spectrometry technology with molecular network analysis and systems biology techniques to elucidate the active ingredients and mechanisms of Shiduqing capsules","authors":"Zhiyan Liu,&nbsp;Shuang Li,&nbsp;Lei Wang,&nbsp;Wei Zhang,&nbsp;Yuanyuan Cao,&nbsp;Chun Bao,&nbsp;Chenning Zhang","doi":"10.1002/rcm.9903","DOIUrl":"10.1002/rcm.9903","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Shiduqing Capsules, a well-known Chinese patent medicine, are widely used clinically for the treatment of pruritus. However, to date, there is a lack of research on its pharmacological substances and mechanisms of action.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>In the current study, the chemical components of Shiduqing Capsules were identified using UHPLC-QE-Orbitrap-MS technology. Molecular network analysis was employed to identify structurally similar compounds to the known chemical components. The potential molecular targets of the active ingredients were predicted using the SwissTargetPrediction website. The identified targets were further analyzed using gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis through the DAVID database. Molecular docking was used to validate the network pharmacology results.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Ultimately, A total of 51 chemical components of Shiduqing Capsules were identified. Molecular network analysis identified 21 flavonoids and 13 terpenoids. The core targets of these ingredients include TP53, AKT1, and STAT3. GO and KEGG enrichment analysis revealed 1,371 different biological functions and 177 signaling pathways. Molecular docking confirmed the high affinity between multiple core active ingredients of Shiduqing Capsules and pruritus targets.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusion</h3>\u0000 \u0000 <p>In conclusion, the effective ingredients of Shiduqing Capsules exert a multifaceted therapeutic effect on pruritus through multiple targets and pathways.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 21","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142091255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross-section for CeO2(g) 利用克努森流出质谱法研究气态锶和钙陶瓷的热力学,并估算 CeO2(g) 的相对电子电离截面。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-08-28 DOI: 10.1002/rcm.9894
Sergey M. Shugurov, Sergey I. Lopatin, Olga A. Zhinkina, Andrej I. Panin, Natalia S. Panina

Rationale

Ceria-based systems are of great interest because of their unique properties. Such systems may be used as anode materials for SOFCs or in oxygen sensors. The exploitation of these materials often requires high temperatures. In such conditions, the partial or complete evaporation of materials is possible. Therefore, knowledge of the values of partial pressures and thermodynamic properties is essential to predict and/or prevent possible consequences and accidents.

Methods

Knudsen effusion mass spectrometry was used to determine partial pressures of vapor species over the SrO–CeO2 and CaO-CeO2 systems. Measurements of partial pressures were performed with a MS-1301 mass spectrometer. Vaporization was carried out using molybdenum or tungsten effusion cells. A theoretical study of gaseous strontium and calcium cerates was performed by several quantum chemical methods: density functional theory (DFT) M06, DFT PBE0, and MP2.

Results

The minimum value of relative electron ionization cross-section for CeO2 was estimated. In the temperature range of 2218–2249 K above the SrO-CeO2 system and of 2128–2208 K above the CaO-CeO2 system, gaseous M, MO, MO, CeO2, O, O2 and MCeO3 (M = Sr, Ca) were found. Energetically favorable structures of gaseous SrCeO3 and CaCeO3 were found, and vibrational frequencies were evaluated in the “rigid rotor-harmonic oscillator” approximation. On the basis of the equilibrium constants of gaseous reaction MO + CeO2 = MCeO3, the standard formation enthalpy of gaseous SrCeO3 (−913 ± 26 kJ/mol) and of gaseous CaCeO3 (−917 ± 26 kJ/mol) at 298 K were determined.

Conclusions

The estimated value of relative electron ionization cross-section for CeO2 is in agreement with the general rule applicable for dioxides. The stability of SrCeO3 and CaCeO3 gaseous species was confirmed by KEMS. Gas-phase reactions involving gaseous SrO (CaO) and CeO2 with gaseous SrCeO3(CaCeO3) were studied. Enthalpy of formation reaction of gaseous SrCeO3(CaCeO3) from gaseous SrO (CaO) were evaluated theoretically, and the obtained value is in agreement with the experimental one.

理由:铈基系统因其独特的性能而备受关注。此类系统可用作 SOFC 的阳极材料或氧气传感器。利用这些材料通常需要高温。在这种条件下,材料有可能部分或完全蒸发。因此,了解分压值和热力学性质对于预测和/或预防可能出现的后果和事故至关重要:方法:采用克努森流出质谱法测定氧化锶-二氧化铈和氧化钙-二氧化铈体系中蒸气物种的分压。分压的测量使用 MS-1301 质谱仪进行。蒸发是使用钼或钨渗流池进行的。通过几种量子化学方法:密度泛函理论(DFT)M06、DFT PBE0 和 MP2,对气态锶和钙铈进行了理论研究:结果:估算出了 CeO2 的相对电子电离截面最小值。在高于 SrO-CeO2 系统 2218-2249 K 和高于 CaO-CeO2 系统 2128-2208 K 的温度范围内,发现了气态 M、MO、MO、CeO2、O、O2 和 MCeO3(M = Sr、Ca)。发现了气态 SrCeO3 和 CaCeO3 的能量有利结构,并按照 "刚性转子-谐振子 "近似方法评估了振动频率。根据气态反应 MO + CeO2 = MCeO3 的平衡常数,确定了 298 K 时气态 SrCeO3 的标准形成焓(-913 ± 26 kJ/mol)和气态 CaCeO3 的标准形成焓(-917 ± 26 kJ/mol):结论:CeO2 的相对电子电离截面估计值与适用于二恶英的一般规则一致。KEMS 证实了 SrCeO3 和 CaCeO3 气态物质的稳定性。研究了气态 SrO(CaO)和 CeO2 与气态 SrCeO3(CaCeO3)的气相反应。对气态 SrO (CaO) 形成气态 SrCeO3(CaCeO3) 的反应焓进行了理论评估,所得值与实验值一致。
{"title":"Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross-section for CeO2(g)","authors":"Sergey M. Shugurov,&nbsp;Sergey I. Lopatin,&nbsp;Olga A. Zhinkina,&nbsp;Andrej I. Panin,&nbsp;Natalia S. Panina","doi":"10.1002/rcm.9894","DOIUrl":"10.1002/rcm.9894","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Ceria-based systems are of great interest because of their unique properties. Such systems may be used as anode materials for SOFCs or in oxygen sensors. The exploitation of these materials often requires high temperatures. In such conditions, the partial or complete evaporation of materials is possible. Therefore, knowledge of the values of partial pressures and thermodynamic properties is essential to predict and/or prevent possible consequences and accidents.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Knudsen effusion mass spectrometry was used to determine partial pressures of vapor species over the SrO–CeO<sub>2</sub> and CaO-CeO<sub>2</sub> systems. Measurements of partial pressures were performed with a MS-1301 mass spectrometer. Vaporization was carried out using molybdenum or tungsten effusion cells. A theoretical study of gaseous strontium and calcium cerates was performed by several quantum chemical methods: density functional theory (DFT) M06, DFT PBE0, and MP2.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The minimum value of relative electron ionization cross-section for CeO<sub>2</sub> was estimated. In the temperature range of 2218–2249 K above the SrO-CeO<sub>2</sub> system and of 2128–2208 K above the CaO-CeO<sub>2</sub> system, gaseous M, MO, MO, CeO<sub>2</sub>, O, O<sub>2</sub> and MCeO<sub>3</sub> (M = Sr, Ca) were found. Energetically favorable structures of gaseous SrCeO<sub>3</sub> and CaCeO<sub>3</sub> were found, and vibrational frequencies were evaluated in the “rigid rotor-harmonic oscillator” approximation. On the basis of the equilibrium constants of gaseous reaction MO + CeO<sub>2</sub> = MCeO<sub>3</sub>, the standard formation enthalpy of gaseous SrCeO<sub>3</sub> (−913 ± 26 kJ/mol) and of gaseous CaCeO<sub>3</sub> (−917 ± 26 kJ/mol) at 298 K were determined.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>The estimated value of relative electron ionization cross-section for CeO<sub>2</sub> is in agreement with the general rule applicable for dioxides. The stability of SrCeO<sub>3</sub> and CaCeO<sub>3</sub> gaseous species was confirmed by KEMS. Gas-phase reactions involving gaseous SrO (CaO) and CeO<sub>2</sub> with gaseous SrCeO<sub>3</sub>(CaCeO<sub>3</sub>) were studied. Enthalpy of formation reaction of gaseous SrCeO<sub>3</sub>(CaCeO<sub>3</sub>) from gaseous SrO (CaO) were evaluated theoretically, and the obtained value is in agreement with the experimental one.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 21","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142091256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Rapid Communications in Mass Spectrometry
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