Rapid Communications in Mass Spectrometry最新文献_第4页

Mass Spectral Studies of N,N-Dialkylacetimidamides Using ESI-HRMS and MS/MS 用ESI-HRMS和MS/MS研究N，N-二烷基乙酰胺的质谱。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-23 DOI: 10.1002/rcm.70015

S. Babu Dadinaboyina, Pranay Renukuntla, Ramunaidu Addipilli, Nikita Singh M, Manasa Masna, Sandhya Bobbali, Swarajya Lakshmi Vattem Venkata, Srinivas Kantevari, Jagadeshwar Reddy Thota

Rationale

For global safety, an effective control and usage of chemical toxins related to chemical warfare agents (CWAs) is of critical importance. Rapid identification of these toxins, their degradation products, and synthetic precursors across various sample matrices is essential. This study focuses on the swift and trace-level identification of N,N-dialkylacetimidamides (amidines), which serve as both precursors and degradation products of Novichoks. These chemicals are listed as nonscheduled reportable chemicals (Schedule 1.A.13 and 1.A.14) under the Chemical Weapon Convention (CWC) by the Organisation for the Prohibition of Chemical Weapons (OPCW).

Method

A high-resolution positive ion mode electrospray ionization tandem mass spectrometry (ESI-HRMS and MS/MS) is employed for the identification and structural characterization of a series of amidines (1–10).

Results

The product ion spectra of all the amidines showed common fragment ions corresponding to [C₂H₄N]⁺, [MH-C₂H₃N]⁺, and [MH-R₂NH₂]⁺. Characterization of isomeric compounds was accomplished by unique fragment ions and differences in the relative intensity of common fragment ions at a collision energy (20 eV). These data have been successfully utilized for the identification of N,N-diisopropylacetimidamide and N-methyl-N-propylacetimidamide in the 56th and 57th OPCW official proficiency test samples, respectively.

Conclusion

A series of amidines (1–10) including three isomeric sets (3–5, 6–7, and 8–10) were synthesized and characterized by ESI-HRMS and MS/MS, and nuclear magnetic resonance (¹H NMR) spectroscopic methods. All the isomeric compounds were differentiated based on their tandem mass spectral data. This method was successfully demonstrated to identify spiked amidines in the 56th and 57th OPCW official proficiency test samples.

理由：为了全球安全，有效控制和使用与化学战剂有关的化学毒素至关重要。快速鉴定这些毒素、它们的降解产物和各种样品基质的合成前体是必不可少的。本研究主要对诺维乔克的前体和降解产物N，N-二kylacetimidamides （amidines）进行快速和痕量鉴定。这些化学品被列为非附表须报告化学品（附表1.A）。1.选a。14)禁止化学武器组织（禁化武组织）的《化学武器公约》（CWC）。方法：采用高分辨率正离子模式电喷雾串联质谱（ESI-HRMS和MS/MS）对一系列脒类化合物（1-10）进行鉴定和结构表征。结果：各脒类产物离子谱均为[C2H4N]+、[MH-C2H3N]+和[MH-R2NH2]+对应的共同片段离子。异构体化合物的表征是通过独特的碎片离子和在碰撞能量（20 eV）下共同碎片离子相对强度的差异来完成的。这些数据已分别成功用于鉴定第56次和57次OPCW官方熟练度测试样品中的N，N-二异丙基乙酰氨基甲酰胺和N-甲基-N-丙基乙酰氨基甲酰胺。结论：合成了包括3-5、6-7和8-10三个同分异构体的一系列脒类化合物（1-10），并采用ESI-HRMS、MS/MS和核磁共振（1H NMR）等方法对其进行了表征。所有的同分异构体化合物根据它们的串联质谱数据进行了区分。该方法已成功地用于鉴定第56和57个禁化武组织官方熟练度测试样品中的加标脒。

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引用次数: 0

Pepsin Digestion for Proteomic Studies of the Human Hair Shaft 人毛干蛋白质组学研究中的胃蛋白酶消化。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-23 DOI: 10.1002/rcm.70018

Darian H. Yee, Rustam Mukhtarov, Aashi D. Sharma, Chen Lin, Bingyun Sun

Rationale

Human hair shafts have received increased research interest owing to their easy accessibility and potential as a window for human health. Because the most abundant component in hair is protein, proteomics is a promising tool for studying the molecular composition of hair shafts. As one of the most sophisticated biomaterials, hair shafts also possess unique structures, particularly keratin intermediate filaments, posing challenges for proteomic sample processing. Previously, we discovered that incomplete trypsin proteolysis increased keratin sequence coverage but resulted in an abnormal stoichiometry between types I and II cuticular keratins (PMCID: 12130615).

Methods

In the present study, we explored the potential to re-examine the human hair proteome through pepsin proteolysis and evaluate whether the previously observed type II to type I keratin ratio was due to enzyme biases introduced particularly by trypsin digestion.

Results

After optimizing the pepsin digestion conditions, we not only confirmed that previous bias was indeed contributed by trypsin but also discovered that pepsin was more effective at identifying keratin-associated proteins, another main protein component than keratins in human hair shafts.

Conclusions

Spectral counting on trypsin-based proteomics has been widely used to study the stoichiometry of protein complexes. For the first time, we confirmed a large bias caused by the trypsin enzyme in spectral counting. We further demonstrated that the use of pepsin can effectively correct such bias. In addition, we discovered that pepsin digestion can better identify keratin-associated proteins than trypsin proteolysis, which offers another effective tool for studying the hair proteome.

理由：人类毛干因其易于获取和作为人类健康窗口的潜力而受到越来越多的研究兴趣。由于头发中最丰富的成分是蛋白质，蛋白质组学是研究毛干分子组成的一种很有前途的工具。作为最复杂的生物材料之一，毛干也具有独特的结构，特别是角蛋白中间丝，这对蛋白质组学样品的处理提出了挑战。先前，我们发现不完全胰蛋白酶蛋白水解增加了角蛋白序列覆盖率，但导致I型和II型角质层角蛋白之间的化学计量异常（PMCID: 12130615）。方法：在本研究中，我们探索了通过胃蛋白酶蛋白水解重新检测人类头发蛋白质组的可能性，并评估了之前观察到的II型和I型角蛋白比率是否由于胰蛋白酶消化引起的酶偏差。结果：在优化胃蛋白酶消化条件后，我们不仅证实了先前的偏差确实是胰蛋白酶造成的，而且发现胃蛋白酶在鉴定人毛干中另一种比角蛋白更有效的主要蛋白质成分角蛋白相关蛋白。结论：基于胰蛋白酶的蛋白质组学光谱计数已广泛应用于蛋白质复合物的化学计量学研究。我们首次证实了胰蛋白酶在光谱计数中引起的较大偏差。我们进一步证明，使用胃蛋白酶可以有效地纠正这种偏差。此外，我们发现胃蛋白酶消化比胰蛋白酶蛋白酶水解能更好地识别角蛋白相关蛋白，这为研究头发蛋白质组提供了另一种有效的工具。

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引用次数: 0

Detection and Characterization of Plasma-Generated Stannane: Influence of Surface Composition on Species Formation 等离子体生成锡烷的检测和表征：表面成分对物质形成的影响。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-22 DOI: 10.1002/rcm.70013

Joshua Rieger, Thorsten Benter, Hendrik Kersten

In extreme ultraviolet (EUV) light sources for lithography, tin droplets are used as target material and evaporate during plasma generation, leading to tin deposition on surrounding surfaces. A widely used method to remove surface-bound tin involves exposure to hydrogen plasma, resulting in the formation of stannane (SnH₄). As a volatile compound, stannane is efficiently pumped out of the system; however, it may also decompose upon contact with surfaces, potentially leading to secondary tin contamination. Despite its relevance in this field, the pathways of stannane formation and decomposition remain only partially understood. Owing to the near absence of mass spectrometric data, comprehensive reference measurements had to be established as part of this study. Mass spectrometry proves to be a suitable technique for the analysis and characterization of tin hydrides, as previously outlined. In order to better understand the etching mechanism of elemental tin exposed to a hydrogen plasma, a laboratory-scale experiment was performed to identify and characterize both neutral and ionic tin hydride compounds. All ten natural isotopes of tin, along with tin hydride fragments, are exhibited by the experimental mass spectra. These species are observed as both native ions, which are formed directly in the plasma, and secondary products, which are generated through electron ionization within the ion source. The relative distribution of the fragments is calculated from the isotopically superimposed mass signals using the custom analysis program RASP. The results of the experimental analysis demonstrate the notable presence of oxygen-containing species in the plasma-generated stannanes. It is of particular significance that our findings underscore the importance of surface reactions in the formation of these oxygenated species, offering valuable insights into the complexities of plasma-surface interactions.

在极紫外（EUV）光刻光源中，锡滴作为靶材料，在等离子体产生过程中蒸发，导致锡沉积在周围表面。一种广泛使用的去除表面结合锡的方法涉及暴露于氢等离子体，导致锡烷（SnH4）的形成。作为一种挥发性化合物，锡烷被有效地泵出系统；然而，它也可能在接触表面时分解，潜在地导致二次锡污染。尽管它在这个领域的相关性，锡烷的形成和分解的途径仍然只是部分了解。由于几乎没有质谱数据，因此必须建立全面的参考测量作为本研究的一部分。质谱法被证明是一种适合分析和表征锡氢化物的技术，如前所述。为了更好地了解元素锡暴露在氢等离子体中的蚀刻机理，进行了实验室规模的实验，以鉴定和表征中性和离子型氢化锡化合物。锡的所有十种天然同位素以及锡氢化碎片都被实验质谱所证实。这些物质被观察为直接在等离子体中形成的原生离子和通过离子源内的电子电离产生的二次产物。利用自定义的分析程序RASP从同位素叠加的质量信号中计算出碎片的相对分布。实验分析结果表明，在等离子体生成的锡烷中存在明显的含氧物质。特别重要的是，我们的发现强调了表面反应在这些氧化物质形成中的重要性，为等离子体表面相互作用的复杂性提供了有价值的见解。

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引用次数: 0

Correction to “Stable Isotope Reference Materials and Scale Definitions—Outcomes of the 2024 IAEA Experts Meeting” 对“稳定同位素标准物质和标度定义——2024年国际原子能机构专家会议成果”的更正。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-19 DOI: 10.1002/rcm.70017

Camin, F., Besic, D., Brewer, P., Allison, C., Coplen, T., Dunn, P., Gehre, M., Gröning, M., Meijer, H.-A.-J, Hélie, J.-F., Iacumin, P., Kraft, R., Krajnc, B., Kümmel, S., Lee, S., Meija, J., Mester, Z., Mohn, J., Moossen, H., Qi, H., Skrzypek, G., Sperlich, P., Viallon, J., Wassenaar, L. and Wielgosz, R. (2025). Stable Isotope Reference Materials and Scale Definitions—Outcomes of the 2024 IAEA Experts Meeting. Rapid Commun Mass Spectrom, 39: e10018, https://doi.org/10.1002/rcm.10018.

We apologize for this error.

The CIAAW-IUPAC endorsed all isotope delta scale definitions appearing in Camin et al. (2025) and agreed to publish the current and all future updates and corrections to these definitions on its website (www.ciaaw.org).

Camin， F., Besic， D., Brewer， P., Allison， C., Coplen， T., Dunn， P., Gehre， M., Gröning， M., Meijer， H.-A。-J, hsamlie, j - f。， Iacumin， P., Kraft， R., Krajnc， B., k mmel， S., Lee， S., Meija， J., Mester， Z., Mohn， J., Moossen， H., Qi， H., Skrzypek， G., Sperlich， P., Viallon， J., Wassenaar， L.和Wielgosz， R.（2025）。稳定同位素标准物质和标度定义——2024年国际原子能机构专家会议成果。快速共质谱，39:e10018, https://doi.org/10.1002/rcm.10018。我们为这个错误道歉。CIAAW-IUPAC认可Camin et al.（2025）中出现的所有同位素三角洲尺度定义，并同意在其网站（www.ciaaw.org）上发布这些定义的当前和未来所有更新和更正。

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引用次数: 0

Wavelength Dependence of fs Laser Ablation Ionisation Mass Spectrometry: a Dedicated Study on NIST SRM 664 激光烧蚀电离质谱的波长依赖性：NIST SRM 664的专用研究。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-16 DOI: 10.1002/rcm.70012

Valentine Grimaudo, Andreas Riedo, Marek Tulej, Peter Wurz

Rationale

Laser ablation mass spectrometry provides fast and direct chemical information of solids with high spatial resolution without the need for complex sample preparation. It has been shown that reducing the laser pulse length below picoseconds improves the quantification of chemical composition measurements of solids. This study compares the impact on chemical quantification of applying femtosecond laser ablation from IR to UV wavelengths to a steel alloy sample from NIST.

Methods

A compact laser ablation ionisation mass spectrometer (LIMS), coupled to a fs laser ablation ion source with a fundamental laser wavelength of 775 nm, is used for the presented mass spectrometric results. The fundamental wavelength is frequency doubled or tripled to 387 and 258 nm, respectively. An extensive mass spectrometric campaign, comprising various laser pulse energies, was conducted using the NIST iron alloy standard reference material 664. The recorded element composition was compared with the NIST certified values.

Results

Chemical composition analysis demonstrated the presence of significant chemical inhomogeneity of the NIST reference samples at spatial scales of about 10 μm, particularly in Ti and S. Large deviations identified were avoided for the presented study. A score was calculated for each of the accumulated spectra, indicating how close the measured composition reflected the certified values. The results show only minor differences between the wavelengths applied for sufficiently high irradiances.

Conclusions

These studies conducted on steel alloy NIST SRM 664 demonstrate that the impact of laser wavelength on the quantification becomes only noticeable for low irradiances. At sufficiently high laser irradiances at around 3.1 TW/cm² and beyond, comparable calibration coefficients can be observed.

原理：激光烧蚀质谱法提供快速和直接的固体化学信息，具有高空间分辨率，无需复杂的样品制备。研究表明，将激光脉冲长度减小到皮秒以下可以提高固体化学成分测量的定量。本研究比较了应用飞秒激光烧蚀从红外到紫外波长对NIST的钢合金样品的化学定量的影响。方法：采用紧凑型激光烧蚀电离质谱仪（LIMS），与基本激光波长为775 nm的fs激光烧蚀离子源耦合，得到质谱分析结果。基本波长的频率分别是387 nm和258 nm的两倍或三倍。使用NIST铁合金标准参考物质664进行了广泛的质谱分析，包括各种激光脉冲能量。将记录的元素组成与NIST认证值进行比较。结果：化学成分分析表明，NIST参考样品在约10 μm的空间尺度上存在显著的化学不均匀性，特别是在Ti和s中。计算每个累积光谱的分数，表明测量成分反映认证值的接近程度。结果表明，用于足够高辐照度的波长之间只有很小的差异。结论：对NIST SRM 664合金钢进行的研究表明，激光波长对定量的影响只有在低辐照度时才会明显。在足够高的激光辐照度（约3.1 TW/cm2及以上）下，可以观察到可比的校准系数。

{"title":"Wavelength Dependence of fs Laser Ablation Ionisation Mass Spectrometry: a Dedicated Study on NIST SRM 664","authors":"Valentine Grimaudo, Andreas Riedo, Marek Tulej, Peter Wurz","doi":"10.1002/rcm.70012","DOIUrl":"10.1002/rcm.70012","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Laser ablation mass spectrometry provides fast and direct chemical information of solids with high spatial resolution without the need for complex sample preparation. It has been shown that reducing the laser pulse length below picoseconds improves the quantification of chemical composition measurements of solids. This study compares the impact on chemical quantification of applying femtosecond laser ablation from IR to UV wavelengths to a steel alloy sample from NIST.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>A compact laser ablation ionisation mass spectrometer (LIMS), coupled to a fs laser ablation ion source with a fundamental laser wavelength of 775 nm, is used for the presented mass spectrometric results. The fundamental wavelength is frequency doubled or tripled to 387 and 258 nm, respectively. An extensive mass spectrometric campaign, comprising various laser pulse energies, was conducted using the NIST iron alloy standard reference material 664. The recorded element composition was compared with the NIST certified values.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Chemical composition analysis demonstrated the presence of significant chemical inhomogeneity of the NIST reference samples at spatial scales of about 10 μm, particularly in Ti and S. Large deviations identified were avoided for the presented study. A score was calculated for each of the accumulated spectra, indicating how close the measured composition reflected the certified values. The results show only minor differences between the wavelengths applied for sufficiently high irradiances.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>These studies conducted on steel alloy NIST SRM 664 demonstrate that the impact of laser wavelength on the quantification becomes only noticeable for low irradiances. At sufficiently high laser irradiances at around 3.1 TW/cm<sup>2</sup> and beyond, comparable calibration coefficients can be observed.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 5","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12707028/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145761765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Comparative In Vitro Metabolic Study of Butonitazene Using Camel Liver and Fungus Cunninghamella elegans for Doping Control Applications 用骆驼肝脏和秀丽隐杆线虫对丁氮唑进行体外代谢比较研究

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-08 DOI: 10.1002/rcm.70005

Ansar Babu Palathinkal, S. Farook Basha, Saraswathy Laya, Jahfar Nalakath, O. K. Praseen, Rasheed Naduvilakkandy, Marina Joseph, Shantymol V. Jose

Rationale

The growing emergence of synthetic opioids in the nitazene subclass such as butonitazene poses a significant challenge for doping control and toxicological monitoring. Butonitazene is a highly potent synthetic opioid, structurally distinct from classical opioids; its potential misuse in competitive events such as horse and camel racing cannot be overlooked. The in vitro metabolism of butonitazene was studied using camel liver, and findings were compared with metabolic profiles obtained from Cunninghamella elegans.

Methods

In vitro metabolic studies of butonitazene were conducted using homogenized camel liver and the fungus Cunninghamella elegans. A liquid chromatography–high resolution mass spectrometry method was used to identify and characterize the metabolites of butonitazene. Extracted metabolites were analyzed on a Thermo Fisher Orbitrap Exploris LC–MS system, renowned for its high resolution and accurate mass detection.

Results

A total of 17 Phase I and one Phase II metabolites were identified. The Phase I metabolism primarily involved N-dealkylation, O-dealkylation, and hydroxylation, whereas the Phase II metabolite was formed through the sulfonation of a hydroxylated Phase I metabolite. These metabolites demonstrate substantial potential as biomarkers for the long-term detection of butonitazene in doping control analysis.

Conclusion

The study utilized advanced high-resolution LC–MS techniques in identifying and characterizing the in vitro metabolites of butonitazene in camels. Given its high potency and its potential for misuse in competitive events, the identified metabolites provide a foundation for effective doping control measures, further enhancing regulatory frameworks designed to protect animal welfare and uphold the integrity of the sport.

随着硝基亚类合成阿片类药物如丁氮唑的出现，对兴奋剂控制和毒理学监测提出了重大挑战。丁氮唑是一种强效的合成阿片类药物，在结构上与传统的阿片类药物不同；它在赛马和骆驼赛等竞技项目中被滥用的可能性不容忽视。利用骆驼肝脏研究了丁氮唑的体外代谢，并将结果与秀丽隐杆线虫的代谢谱进行了比较。方法采用匀质骆驼肝脏和秀丽隐杆线虫进行体外代谢研究。采用液相色谱-高分辨质谱联用方法对丁氮唑的代谢物进行了鉴定和表征。提取的代谢物在Thermo Fisher Orbitrap Exploris LC-MS系统上进行分析，该系统以其高分辨率和准确的质量检测而闻名。结果共鉴定出17个I期代谢物和1个II期代谢物。第一阶段代谢主要涉及n -脱烷基、o -脱烷基和羟基化，而第二阶段代谢物是通过羟基化的第一阶段代谢物的磺化形成的。这些代谢物在兴奋剂控制分析中显示出作为长期检测丁二氮的生物标志物的巨大潜力。结论本研究利用先进的高分辨率LC-MS技术鉴定和表征了布顿他嗪在骆驼体内的体外代谢产物。鉴于其高效力和在竞技赛事中被滥用的可能性，鉴定出的代谢物为有效的兴奋剂控制措施提供了基础，进一步加强了旨在保护动物福利和维护体育诚信的监管框架。

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引用次数: 0

Synthesis of Reference Standards and Optimization of UPLC-ESI-MS/MS Method for Quantification of Organosulfates in PM2.5 PM2.5中有机硫酸盐含量参考标准的合成及UPLC-ESI-MS/MS方法的优化

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-08 DOI: 10.1002/rcm.70008

Zhichao Dong, Subba Rao Devineni, Xiaoli Fu, Zhanjie Xu, Mingyu Li, Pingqing Fu, Cong-Qiang Liu, Chandra Mouli Pavuluri

Rationale

Atmospheric PM_2.5 affects climate by altering radiative forcing and harms human health. Organosulfates (OSs) intensify these impacts, as cloud condensation nuclei modify the radiation balance and increase toxicological risks. We synthesized OSs reference standards and optimized a sensitive UPLC–MS/MS method, enabling precise quantification to mitigate PM_2.5 pollution on climate and health.

Methods

We synthesized five organosulfates (ethyl-, 3-methylbenzyl-, cyclohexyl-, benzyl-, and phenethyl sulfate) as reference standards. These, combined with four commercial standards (methyl-, phenyl-, octyl-, and 4-nitrophenyl sulfate), were quantified by ultra-high performance liquid chromatography coupled with electrospray ionization (ESI) tandem mass spectrometry (UPLC-ESI-MS/MS). Separation used a Waters HSS T3 column with a gradient mobile phase (0.1% formic acid in H₂O/CH₃OH). ESI in negative mode enabled sensitive MS/MS detection.

Results

A nine-point calibration curve ranging from 0.08 to 20 ng mL⁻¹ of standards in solvent was used to establish instrument response. The method was validated by analysis of three replicate environmental samples fortified with 5 ng mL⁻¹ of mixed standard. The recoveries of various OSs were 44%–126%, and their method detection limits were 0.10 ng mL⁻¹ and the method limits of quantification were 0.50 ng mL⁻¹.

Conclusions

The optimized UPLC-ESI-MS/MS method was successfully applied for the determination of various OSs in PM_2.5 collected from Tianjin, China. It enables the precise measurement of OSs in aerosols that provide a critical tool to improve air quality monitoring and develop strategies to reduce pollution-related health impacts.

大气PM2.5通过改变辐射强迫影响气候，危害人类健康。有机硫酸盐（OSs）加剧了这些影响，因为云凝结核改变了辐射平衡并增加了毒理学风险。我们综合了5种参考标准，并优化了一种灵敏的UPLC-MS /MS方法，实现了PM2.5的精确定量，从而减轻了PM2.5对气候和健康的影响。方法合成五种有机硫酸盐（乙基-、3-甲基苄基-、环己基-、苄基-和硫酸苯乙酯）作为参比标准。结合四种商业标准（甲基、苯基、辛基和4-硝基苯硫酸盐），采用超高效液相色谱-电喷雾电离（ESI）串联质谱（UPLC-ESI-MS/MS）进行定量。分离采用Waters HSS T3色谱柱，梯度流动相（0.1%甲酸水溶液/CH3OH）。ESI在阴性模式下使敏感的MS/MS检测。结果在0.08 ~ 20 ng mL−1的标准溶剂中建立9点校准曲线，建立仪器响应。通过分析添加5 ng mL−1混合标准物的三个重复环境样品，验证了该方法。各os的加样回收率为44% ~ 126%，方法检出限为0.10 ng mL−1，定量限为0.50 ng mL−1。结论优化后的UPLC-ESI-MS/MS方法可用于天津地区PM2.5中各种os的测定。它能够精确测量气溶胶中的生态系统，为改善空气质量监测和制定减少与污染有关的健康影响的战略提供重要工具。

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引用次数: 0

Differentiating Δ8-THC and Δ9-THC Isomers: Mass Spectrometry Analysis and Computational Explanation 区分Δ8-THC和Δ9-THC异构体：质谱分析和计算解释

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-08 DOI: 10.1002/rcm.70011

Xing Ke, Xi Chen, Xianxin Chen, Hao Wu, Yilei Fan, Yu Xu, Jiawei Xu

Rationale

Isomerism is common in new psychoactive substances (NPSs). Due to insignificant differences in their structure and properties, NPS isomers are hard to separate and identify, posing challenges for forensic laboratories to accurately identify them. Delta-8-tetrahydrocannabinol (Δ⁸-THC), a double-bond isomer of delta-9-tetrahydrocannabinol (Δ⁹-THC), is synthesized from cannabidiol (CBD).

Methods

To explore the MS fragmentation pattern of Δ⁸-THC and Δ⁹-THC, we systematically investigated them by gas chromatography–quadrupole time-of-flight mass spectrometry (GC-Q-TOF/MS) and liquid chromatography coupled to high-resolution quadrupole Orbitrap mass spectrometry (LC-Q-Orbitrap/MS).

Results

For GC-Q-TOF/MS analysis, significant differences in the ion abundance of the two characteristic ions at m/z 314 and 299 between these two isomers (Δ⁸-THC and Δ⁹-THC) stem from the varied stability of the free radicals they generate after losing an electron. Moreover, the ratio of the ion abundance of the fragment ions at m/z 314 and 299 can be utilized to recognize these two isomers. For LC-Q-Orbitrap/MS analysis, the fragmentation patterns of Δ⁸-THC were similar to those of Δ⁹-THC. Additional investigations by computational study revealed that Δ⁸-THC cationic radical can undergo a stepwise process like a retro Diels–Alder reaction to release an isoprene molecule directly but Δ⁹-THC via a double-hydrogen atoms transfer, shifting the location of carbon–carbon double bond, which indicates the different peaks at m/z 246 of Δ⁸-THC and 231 of Δ⁹-THC in EI-MS fragmentation processes.

Conclusions

Distinguishing accurately between Δ⁸-THC and Δ⁹-THC assists drug laboratories with in-depth analysis of drug sources, providing exact intelligence and scientific support to law enforcement.

基本原理同分异构现象在新型精神活性物质（nps）中很常见。由于NPS异构体的结构和性质差异不大，因此很难分离和鉴定，这给法医实验室准确鉴定它们带来了挑战。δ -8-四氢大麻酚（Δ8-THC）是δ -9-四氢大麻酚（Δ9-THC）的双键异构体，由大麻二酚（CBD）合成。方法采用气相色谱-四极杆飞行时间质谱联用（GC-Q-TOF/MS）和液相色谱-高分辨率四极杆轨道rap质谱联用（LC-Q-Orbitrap/MS）对Δ8-THC和Δ9-THC的质谱破碎模式进行系统研究。结果在GC-Q-TOF/MS分析中，两个同分异构体（Δ8-THC和Δ9-THC）在m/z 314和299处的两个特征离子的离子丰度存在显著差异，这是由于它们在失去电子后产生的自由基的稳定性不同。此外，碎片离子在m/z 314和299处的离子丰度比可以用来识别这两种异构体。LC-Q-Orbitrap/MS分析发现，Δ8-THC的破碎模式与Δ9-THC相似。另外，通过计算研究发现，Δ8-THC阳离子自由基可以像Diels-Alder反应一样，通过步进过程直接释放异戊二烯分子，而Δ9-THC则通过双氢原子转移，改变了碳碳双键的位置，这表明在e- ms裂解过程中，Δ8-THC和Δ9-THC的m/z 246和231处有不同的峰。结论准确区分Δ8-THC和Δ9-THC有助于药物实验室深入分析药物来源，为执法提供准确的情报和科学支持。

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引用次数: 0

Comparative Metabolomic Analysis of Benzyl Adenine and Meta-Topolin Riboside Treatments in “Tainung No. 1” Passion Fruit “台农一号”百香果中苯腺嘌呤和间topolin核苷处理的代谢组学比较分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-08 DOI: 10.1002/rcm.70006

Ying-Chun Chen, Han-Ju Chien, Yi-Feng Zheng, Huey-Ling Lin, Chien-Chen Lai

Rationale

Meta-topolin riboside (mTR) has shown superior effects over benzyladenine (BA) in promoting root and shoot development in passion fruit tissue culture, yet its underlying mechanisms remain unclear. Understanding the metabolic differences between mTR and BA treatments can inform optimized propagation strategies for high-quality planting material in this economically important crop.

Methods

Nodal buds of Passiflora edulis “Tainung No. 1” were cultured on BA- or mTR-supplemented medium, then analyzed using ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) in SWATH acquisition mode. Metabolite features were extracted, statistically filtered (VIP > 1, FC > 1.5 or < 0.667, p < 0.05), identified via multiple databases, and subjected to enrichment and pathway analysis.

Results

SWATH-MS detected 2823 ions in positive and 1637 in negative mode, with 21 significant metabolites identified in each mode. mTR treatment upregulated metabolites linked to root development (e.g., 5,10-methylenetetrahydrofolate, daidzin, and hesperidin) and stem elongation (amygdalin), while BA treatment had higher levels of kinetin, gibberellin A4, and lignans. Pathway analysis highlighted folate metabolism as significantly enriched in mTR samples.

Conclusions

mTR treatment altered phytohormone, flavonoid and phenolic profiles in ways that likely promote rooting, shoot elongation and oxidative stress resilience, explaining its superior growth performance over BA. These insights can guide refined cytokinin use in micropropagation and broader applications in horticultural biotechnology.

在百香果组织培养中，Meta-topolin riboside （mTR）在促进根和梢发育方面的作用优于苯ladenine (BA)，但其机制尚不清楚。了解mTR和BA处理之间的代谢差异可以为这种重要经济作物的优质种植材料的优化繁殖策略提供信息。方法将西番莲“台农1号”的节芽分别培养在BA-或mtr -补充培养基上，采用超高效液相色谱-四极杆飞行时间质谱（UHPLC-QTOF-MS） SWATH采集模式进行分析。提取代谢物特征，进行统计过滤（VIP > 1, FC >； 1.5或<； 0.667, p < 0.05），通过多个数据库进行鉴定，并进行富集和途径分析。结果SWATH-MS在阳性模式下检测到2823个离子，在阴性模式下检测到1637个离子，每种模式下鉴定出21种显著代谢物。mTR处理上调了与根发育相关的代谢物（例如，5,10-亚甲基四氢叶酸、大豆苷和橙皮苷）和茎伸长（苦杏仁苷），而BA处理具有更高水平的动蛋白、赤霉素A4和木脂素。途径分析显示，叶酸代谢在mTR样品中显著富集。结论mTR处理改变了植物激素、类黄酮和酚类物质的分布，可能促进了生根、芽伸长和氧化胁迫恢复能力，解释了其生长性能优于BA的原因。这些见解可以指导细胞分裂素在微繁殖中的精细使用以及在园艺生物技术中的更广泛应用。

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引用次数: 0

Critical Considerations for TOF-SIMS Sample Preparation and Parameter Optimization TOF-SIMS样品制备和参数优化的关键考虑因素

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-08 DOI: 10.1002/rcm.70010

Chuqi Shi, Yanfang Pan, Qin Yang, Yikun Pan

Rationale

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is an ultrasensitive surface analysis technique capable of providing comprehensive elemental and molecular characterization of sample surfaces. The selection of appropriate sample preparation methods and optimal instrument parameters is critical for obtaining accurate and reliable analytical results.

Methods

This article systematically discusses three key aspects of the TOF-SIMS surface analytical technique: essential considerations in sample preparation, optimization of spectral acquisition parameters, and configuration of depth profiling parameters.

Results

Through representative case studies, we elucidate the fundamental principles and practical considerations for TOF-SIMS sample preparation and measurement optimization, thereby establishing a framework for acquiring high-quality TOF-SIMS data.

Conclusions

Sample preparation and processing are critical for ensuring the validity of TOF-SIMS detection results, while selecting appropriate testing parameters facilitates the acquisition of authentic and valid sample information. The presented methodology in this paper serves as a valuable reference for ensuring data reliability in TOF-SIMS analyses.

飞行时间二次离子质谱（TOF-SIMS）是一种超灵敏的表面分析技术，能够提供样品表面的全面元素和分子表征。选择合适的样品制备方法和最佳的仪器参数是获得准确可靠的分析结果的关键。方法系统地讨论了TOF-SIMS表面分析技术的三个关键方面：样品制备的基本考虑、光谱采集参数的优化和深度剖面参数的配置。结果通过代表性案例研究，阐明了TOF-SIMS样品制备和测量优化的基本原则和实际考虑因素，从而建立了获得高质量TOF-SIMS数据的框架。结论样品制备和处理是保证TOF-SIMS检测结果有效性的关键，选择合适的检测参数有助于获得真实有效的样品信息。本文所提出的方法为保证TOF-SIMS分析数据的可靠性提供了有价值的参考。

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引用次数: 0