Rapid Communications in Mass Spectrometry最新文献_第3页

Natural rhenium sulfide clusters formed under conditions of laser desorption-ionization 在激光解吸电离条件下形成的天然硫化铼簇。

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-23 DOI: 10.1002/rcm.9919

Viacheslav V. Lebedev, Daniil I. Yarykin, Ilya V. Chaplygin, Oleg P. Gorelkov, Rinad Kh. Zalavutdinov, Aleksey K. Buryak

Rationale

Cluster forms of rhenium sulfides have important practical applications as catalysts in oil refining and thus present high interest. However, only a limited number of rhenium sulfide clusters have been described previously. It is known that cluster formation actively occurs under conditions of laser desorption–ionization; nevertheless, detailed studies of rhenium sulfides under such conditions were apparently not conducted previously.

Methods

A sample of natural rhenium sulfide, collected from the fumarolic field of Kudriavy volcano (Iturup island, Russia) in 2002, was investigated using the laser desorption–ionization mass spectrometry method. The formed rhenium sulfide clusters were registered by a time-of-flight detector and identified programmatically using the software developed in IPCE RAS. The identification involved a comparison of the distribution of isotopic peak intensities, observed in the resulting mass spectra, with the theoretical probabilities of occurrence of various isotopologues for hypothetical rhenium sulfide species.

Results

Over 60 rhenium sulfide clusters of Re_xS_y⁺ and Re_xS_yO_z⁻ types containing up to 10 rhenium atoms were formed when a sample of natural rhenium sulfide was exposed to laser desorption–ionization conditions. Several isolated heterometallic Re_XMoS_Y⁺ and Re_XMoS_YO_Z⁻ clusters containing up to eight rhenium atoms were additionally observed in the resulting mass spectra. The species with compositions, for which the electrically neutral analogs are known, apparently were the most stable rhenium sulfide clusters among the detected ones.

Conclusions

The obtained data allowed summarizing the patterns of formation of rhenium sulfide clusters under conditions of laser desorption-ionization. The ability of rhenium and sulfur to form cluster species containing from 7 to 10 atoms of rhenium was likely discovered for the first time. The majority of the rhenium sulfide clusters described in this study, notably Re_xS_y⁺ ions containing over seven atoms of rhenium, were apparently not observed previously.

理由：簇状硫化铼作为炼油催化剂具有重要的实际应用价值，因此备受关注。然而，以前描述的硫化铼团簇数量有限。众所周知，在激光解吸电离条件下，簇的形成非常活跃；然而，以前显然没有对这种条件下的硫化铼进行过详细研究：方法：使用激光解吸电离质谱法研究了 2002 年从库德里亚维火山（俄罗斯伊图鲁普岛）的熔岩区采集的天然硫化铼样品。形成的硫化铼簇由飞行时间探测器记录，并使用 IPCE RAS 开发的软件进行程序化识别。鉴定工作包括将质谱中观察到的同位素峰强度分布与假设硫化铼物种的各种同位素出现的理论概率进行比较：将天然硫化铼样品置于激光解吸电离条件下，可形成 60 多种 RexSy + 和 RexSyOz - 型硫化铼簇，其中最多含有 10 个铼原子。此外，在生成的质谱中还观察到了几个孤立的异金属 ReXMoSY + 和 ReXMoSYOZ - 簇，其中最多含有 8 个铼原子。在检测到的硫化铼团簇中，具有已知电中性类似物成分的物种显然是最稳定的：所获得的数据有助于总结在激光解吸电离条件下硫化铼簇的形成模式。铼和硫能够形成含有 7 至 10 个铼原子的团簇物种，这可能是首次发现。本研究中描述的大多数硫化铼簇，特别是含有超过 7 个铼原子的 RexSy + 离子，以前显然没有观察到。

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引用次数: 0

Separation of mycolic acid isomers by cyclic ion mobility-mass spectrometry 利用环离子迁移质谱法分离霉菌酸异构体。

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-23 DOI: 10.1002/rcm.9917

Hector de las Heras Prieto, Laura M. Cole, Sarah Forbes, Martin Palmer, Rachel Schwartz-Narbonne

Rationale

Mycobacterial species contain high concentrations of mycolic acids in their cell wall. Mycobacteria can pose a threat to both human health and the environment. Mass spectrometry lipidomic characterization can identify bacterial species and suggest targets for microbiological interventions. Due to the complex structures of mycolic acids and the possibility of isobaric isomers, multiple levels of separation are required for complete characterization. In this study, cyclic ion mobility (cIM) mass spectrometry (MS) was used for the analysis, separation and fragmentation of mycolic acids isomers from the bacterial species Gordonia amarae and Mycobacterium bovis.

Methods

Mycolic acid isomers were interrogated from cultured G. amarae biomass and commercially available M. bovis mycolic acid extracts. These were infused into a cIM-enabled quadrupole time-of-flight MS. Ions of interest were non-simultaneously selected with the quadrupole and passed around the cyclic ion mobility device multiple times. Fragment ion analysis was then performed for the resolved isomers of the quadrupole-selected ions.

Results

Repeated passes of the cIM device successfully resolved otherwise overlapping MA isomers, allowing isomer isolation and producing an ion-specific post-mobility fragmentation spectrum without isomeric interference.

Conclusions

Mycolic acids (MA) isomers from G. amarae and M. bovis were resolved, resulting in a high mobility resolution and low interference fragmentation analysis. These revealed varying patterns of MA isomers in the two species: G. amarae's most abundant ion of each set of MA has 1–2 conformations, while the MA + 2 m/z the most abundant ion of each set has 3–6 conformations. These were resolved after 70 passes of the cyclic device. M. bovis' most abundant ion of each keto-MA set has 2 conformations, while the keto-MA + 2 m/z has 1–2 conformations. These were resolved after 75 passes.

理由分枝杆菌的细胞壁中含有高浓度的霉菌酸。分枝杆菌会对人类健康和环境造成威胁。质谱脂质体特征描述可以确定细菌种类，并提出微生物干预的目标。由于霉菌醇酸结构复杂，可能存在同分异构体，因此需要多层次分离才能完成表征。本研究采用循环离子淌度（cIM）质谱（MS）分析、分离和碎裂细菌物种戈登菌和牛分枝杆菌的霉菌酚酸异构体：方法：从培养出的羊角藻生物质和市售的牛分枝杆菌霉菌酸提取物中检测霉菌酸异构体。这些物质都被注入到支持 cIM 的四极杆飞行时间质谱中。感兴趣的离子在四极杆上进行非同时选择，并在循环离子淌度装置上循环多次。然后对四极杆选择离子的解析异构体进行碎片离子分析：结果：重复通过 cIM 装置成功地分辨出了原本重叠的 MA 异构体，从而实现了异构体的分离，并在没有异构体干扰的情况下产生了离子特异的迁移后碎片谱：结论：通过高迁移率分辨和低干扰碎片分析，成功分辨出了G. amarae和M. bovis中的霉菌醇酸（MA）异构体。分析结果表明，这两个物种的霉酚酸异构体模式各不相同：G.amarae的每组MA中最丰富的离子有1-2种构象，而MA + 2 m/z每组中最丰富的离子有3-6种构象。经过 70 次循环装置后，这些构象得到了解析。牛海绵状芽孢杆菌的每组酮-MA 中最丰富的离子有 2 种构象，而酮-MA + 2 m/z 有 1-2 种构象。经过 75 次循环后，这些构象得到了解决。

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引用次数: 0

High temperature mass spectrometric studies over Zr-Al binary system: Thermodynamic properties over and biphasic regions 锆铝二元体系的高温质谱研究：双相和双相区域的热力学性质

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-22 DOI: 10.1002/rcm.9914

Vinjavarapu Venkata Trinadh, Suranjan Bera, Cherukuri Venkata Siva Brahmananda Rao

Vaporisation thermodynamic studies were performed over <ZrAl₃(cr) + ZrAl₂(cr) > and <ZrAl₂(cr) + Zr₂Al₃(cr) > biphasic region of Al-Zr system by employing Knudsen Effusion Mass Spectrometry (KEMS) in the temperature range between 1,233 to 1,535 and 1,208 to 1,458 K, respectively. It was observed that these samples undergo incongruent vaporisation with Al(g) alone in the vapour phase. Following are the recommended p–T relations deduced in the present study:

log (p_Al/Pa) = (−18,663 ± 132)/T + (12.23 ± 0.10) (1,233–1,535 K) < ZrAl₃(cr) + ZrAl₂(cr)>.

log (p_Al/Pa) = (−18,982 ± 112)/T + (11.92 ± 0.08) (1,208–1,458 K) < ZrAl₂(cr) + Zr₂Al₃(cr)>.

From the p–T and K-T relations, based on the second and third law methods of thermodynamics, the enthalpy changes of the following reactions were evaluated: ZrAl₃(cr) = ZrAl₂(cr) + Al(g) and 2ZrAl₂(cr) = Zr₂Al₃(cr) + Al(g). Subsequently, the enthalpies of the formation of ZrAl₂(cr) and Zr₂Al₃(cr) were deduced.

在 1233 至 1535 K 和 1208 至 1458 K 的温度范围内，采用克努森喷射质谱法 (Knudsen Effusion Mass Spectrometry, KEMS) 分别对 Al-Zr 系统的 <ZrAl3(cr) + ZrAl2(cr) > 和 <ZrAl2(cr) + Zr2Al3(cr) > 双相区进行了汽化热力学研究。据观察，这些样品在气相中与单独的 Al(g) 发生了不一致的汽化。以下是本研究推导出的建议 p-T 关系：log (pAl/Pa) = (-18,663 ± 132)/T + (12.23 ± 0.10) (1,233-1,535 K) < ZrAl3(cr) + ZrAl2(cr)>.log (pAl/Pa) = (-18,982 ± 112)/T + (11.92 ± 0.08) (1,208-1,458 K) < ZrAl2(cr) + Zr2Al3(cr)>.log (pAl/Pa) = (-18,982 ± 112)/T + (11. ± 0.08) (1,208-1,458 K) < ZrAl2(cr) + Zr2Al3(cr)>：ZrAl3(cr) = ZrAl2(cr) + Al(g) 和 2ZrAl2(cr) = Zr2Al3(cr) + Al(g)。随后，推导出了 ZrAl2(cr) 和 Zr2Al3(cr) 的生成焓。

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引用次数: 0

Equine metabolic investigation of the phosphodiesterase-4 inhibitor ibudilast as a potential performance enhancer 将磷酸二酯酶-4抑制剂伊布司特作为一种潜在的运动表现提升剂的马匹代谢研究。

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-22 DOI: 10.1002/rcm.9916

Moses Philip, Abdul Khader Karakka Kal, Michael Benedict Subhahar, Tajudheen K. Karatt, Fatma Mohammed Graiban, Meleparappil Muhammed Ajeebsanu, Marina Joseph, Shantymol V. Jose

Rationale

Phosphodiesterase 4 (PDE4) inhibitors are a newer class of drugs that induce bronchodilation and have anti-inflammatory effects, making them susceptible to misuse as performance enhancers in competitive sports.

Methods

This study explores the metabolic conversion of PDE4 inhibitor ibudilast in thoroughbred horses after oral administration and in vitro using equine liver microsomes and Cunninghamella elegans. A liquid chromatography-high resolution mass spectrometry method was used to postulate the plausible structures of the detected metabolites.

Results

A total of 20 in vivo metabolites were identified under experimental conditions, including 12 Phase I and 8 Phase II conjugated metabolites. Phase I metabolites were predominantly formed through hydroxylation (mono-, di-, and tri-hydroxylation). Demethylated metabolites were also identified during this investigation. Additionally, the research detected Phase II metabolites conjugated with glucuronic and sulfonic acids.

Conclusions

The data presented here can assist in detecting the PDE4 inhibitor ibudilast and uncover its illicit use in competitive sports.

理由：磷酸二酯酶4（PDE4）抑制剂是一类较新的药物，可诱导支气管扩张并具有抗炎作用，因此在竞技体育中容易被误用为提高成绩的药物：本研究利用马肝脏微粒体和昆明马杆菌，探讨了纯血马口服 PDE4 抑制剂依布司特后在体外的代谢转化。采用液相色谱-高分辨质谱法推测检测到的代谢物的合理结构：结果：在实验条件下，共鉴定出 20 种体内代谢物，包括 12 种第一阶段代谢物和 8 种第二阶段共轭代谢物。第一阶段代谢物主要是通过羟基化（一羟基化、二羟基化和三羟基化）形成的。调查中还发现了脱甲基代谢物。此外，研究还发现了与葡萄糖醛酸和磺酸共轭的第二阶段代谢物：本文提供的数据有助于检测 PDE4 抑制剂依布地司特，并揭露其在竞技体育中的非法使用。

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引用次数: 0

An optimised method to isotopically label pure synthetic peptides ‘in-house’ for absolute quantification in bottom-up proteomics 内部 "同位素标记纯合成肽的优化方法，用于自下而上蛋白质组学的绝对定量分析

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-17 DOI: 10.1002/rcm.9892

Nikita Bhakta, Colleen B. Maxwell, Shimon Atunde, Jatinderpal K. Sandhu, Oliver C. Slingsby, Emer M. Brady, Donald J. L. Jones, Leong L. Ng

Rationale

Heavy-labelled internal standards increasingly represent the gold standard for absolute quantitation in mass spectrometry (MS)-based bottom-up proteomics. The biggest drawbacks of using these standards are that they have high costs and lengthy lead times.

Methods

We describe an efficient, low-cost optimised method to enable ‘in-house’ heavy labelling of synthetic tryptic peptides for absolute quantification using tandem LC-MS/MS mass spectrometry. Our methodology uses 18O water in a trypsin-catalysed oxygen exchange reaction at the carboxyl terminus with the overall aim of reducing the costs and lead time associated with sourcing heavy standards from commercial vendors.

Results

Step-by-step instructions are provided on how to execute this protocol with high-throughput adaptations utilising a 96-well plate and a liquid-handling robot. Detailed notes on experimental setup, tips for troubleshooting and suggested improvements to maximise labelling efficiencies are highlighted to achieve the best results. Under optimum conditions, labelling efficiencies of peptides can reach from 95% to 100%.

Conclusions

The application of the ‘in-house’ labelled standards in generating calibration curves to quantify endogenous peptide concentrations is just as effective as using the synthetically sourced standards while also having great cost reduction implications as well as saving time spent waiting for peptides to arrive. The protocol is highly adaptable and can be customized to fit the specific setup of any laboratory, maximizing achievable labelling efficiencies.

理论依据在基于质谱（MS）的自下而上蛋白质组学研究中，重标记内标日益成为绝对定量的黄金标准。使用这些标准的最大缺点是成本高、周期长。方法我们介绍了一种高效、低成本的优化方法，可对合成胰蛋白酶肽进行 "内部 "重标记，以便使用串联 LC-MS/MS 质谱进行绝对定量。我们的方法在羧基末端的胰蛋白酶催化的氧交换反应中使用 18O 水，总体目标是降低成本，缩短从商业供应商处采购重标准物质所需的时间。结果逐步说明了如何利用 96 孔板和液体处理机器人进行高通量调整来执行该方案。详细说明了实验设置、故障排除技巧和改进建议，以最大限度地提高标记效率，从而获得最佳结果。在最佳条件下，多肽的标记效率可达 95% 至 100%。结论应用 "内部 "标记的标准品生成校准曲线来量化内源性肽的浓度，与使用合成标准品一样有效，同时还能大大降低成本，节省等待肽到达的时间。该方案适应性强，可根据任何实验室的具体设置进行定制，最大限度地提高可实现的标记效率。

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引用次数: 0

Reference-free thio-succinimide isomerization characterization by electron-activated dissociation 通过电子激活解离进行无参照物硫代琥珀酰亚胺异构化表征

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-17 DOI: 10.1002/rcm.9910

Junyan Yang, Jiaqi Yuan, Yue Huang, Anton I. Rosenbaum

Rationale

Isomerism can be an important aspect in pharmaceutical drug development. Identification of isomers can provide insights into drug pharmacology and contribute to better design of drug molecules. The general approaches to differentiate isomers include Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and circular dichroism. Additionally, a commonly used method to differentiate isomers is liquid chromatography coupled with mass spectrometry (LC-MS). Notably, LC-MS is routinely applied to leucine and isoleucine differentiation to facilitate protein sequencing. This work focuses on isomer differentiation of widely employed thio-succinimide structure bridging the antibody backbone and linker-payload of antibody-drug conjugates (ADCs). Thio-succinimide hydrolysis stabilizes the payload-protein structure while generating a pair of constitutional isomers: thio-aspartyl and thio-isoaspartyl.

Methods

This paper introduces a hybrid method using ligand binding assay (LBA) and liquid chromatography coupled with tandem MS (LC–MS/MS) to reveal isomerization details of thio-succinimide hydrolysis over time in plasma samples incubated with ADC. Application of two orthogonal dissociation methods, collision-induced dissociation (CID) and electron-activated dissociation (EAD) revealed different MS/MS spectra for this pair of isomers. This observation enables a unique approach in distinguishing thio-succinimide hydrolysis isomers.

Results

We observed signature [R₁ + Thio + 57 + H]⁺, [R₂ + Succ + H₂O − 57 + H]⁺, and [R₂ + Succ + H₂O − 44 + 2H]²⁺ product ions (Succ = succinimide) that differentiated thio-aspartyl and thio-isoaspartyl isomers using EAD. A newly discovered [R₂ + ThioSucc + H₂O − 44 + 2H]²⁺ ion also served as additional evidence that further supported our findings.

Conclusions

This study is a first-to-date identification of thio-succinimide hydrolysis isomers without using synthesized reference materials. This approach should be applicable to all thio-succinimide-linked molecules. Correct identification of thio-succinimide hydrolysis isomers may eventually benefit the development of ADCs in the future.

理论依据异构体是药物开发的一个重要方面。同分异构体的鉴定可为药物药理学提供见解，有助于更好地设计药物分子。区分异构体的一般方法包括傅立叶变换红外光谱法（FTIR）、核磁共振法（NMR）和圆二色法。此外，液相色谱-质谱法（LC-MS）也是区分异构体的常用方法。值得注意的是，液相色谱-质谱法通常用于区分亮氨酸和异亮氨酸，以促进蛋白质测序。这项工作的重点是对广泛使用的硫代琥珀酰亚胺结构进行异构体分化，该结构是抗体药物共轭物（ADC）的抗体骨架和连接载体之间的桥梁。硫代琥珀酰亚胺水解可稳定有效载荷-蛋白质结构，同时产生一对构型异构体：硫代天冬氨酰和硫代异天冬氨酰。方法本文介绍了一种使用配体结合测定（LBA）和液相色谱-串联质谱（LC-MS/MS）的混合方法，以揭示硫代琥珀酰亚胺在与 ADC 培养的血浆样本中随时间水解的异构化细节。应用碰撞诱导解离（CID）和电子激活解离（EAD）这两种正交解离方法揭示了这对异构体的不同 MS/MS 光谱。这一观察结果为区分硫代琥珀酰亚胺水解异构体提供了一种独特的方法。结果我们观察到了特征性的[R1 + Thio + 57 + H]+、[R2 + Succ + H2O - 57 + H]+和[R2 + Succ + H2O - 44 + 2H]2+产物离子（Succ = 琥珀酰亚胺），利用 EAD 区分了硫代天冬氨酰和硫代异天冬氨酰异构体。新发现的[R2 + ThioSucc + H2O - 44 + 2H]2+离子也是进一步支持我们研究结果的额外证据。结论本研究是迄今为止首次在不使用合成参考材料的情况下鉴定硫代琥珀酰亚胺水解异构体的研究。这种方法适用于所有硫代琥珀酰亚胺连接的分子。正确鉴定硫代琥珀酰亚胺水解异构体可能最终有利于未来 ADC 的开发。

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引用次数: 0

Utilizing ESI-MS/MS and ion mobility spectrometry for structural characterization and isomer differentiation of 1, 2-unsaturated (1-4) linked disaccharide derivatives and their 2-C-functionalized analogues 利用 ESI-MS/MS 和离子迁移谱对 1、2-不饱和 (1-4) 连接二糖衍生物及其 2-C 功能化类似物进行结构表征和异构体区分

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-12 DOI: 10.1002/rcm.9899

Ines Starke, Sylvia Fürstenberg, Steffen Thomas

Rationale

The 1, 2-unsaturated derivatives of (1-4) linked disaccharides serve as versatile building blocks for synthesizing biologically active compounds. Distinguishing between four pairs of stereoisomers in mixtures presents a challenging task. In this study, disaccharide derivatives are analyzed as alkali metal adducts using electrospray ionization tandem mass spectrometry (ESI-MS/MS), both as individual compounds and in mixtures by ion mobility mass spectrometry (IMS).

Methods

Electrospray ionization (ESI) in combination with tandem mass spectrometry (MS/MS) in positive mode was employed to differentiate lithium adduct ions of hexa-acetyl/hexa-benzyl-D-lactals, and hexa-acetyl/hexa-benzyl-D-maltals, along with their corresponding 2-C-branched malonates. The high resolving power of trapped ion mobility spectrometry (TIMS) with the imeX™ functionality rapidly identified different metal adducts (Li, Na, Cs) as individual isomers and separated mixtures of stereoisomers. The measured collisional cross section (CCS) values were analyzed in relation to predicted CCS values.

Results

MS/MS spectra of the [M + Li]⁺ ions of glycal disaccharide analogues exhibited typical cross-ring and glycosidic bond cleavages. Collision-induced dissociation (CID) spectra provided insights into their fragmentation behavior, allowing differentiation of (1-4) linked disaccharides. TIMS technology delivered adjustable ion mobility resolution for suitable separation of the four sets of stereo isomeric compounds. However, accurately predicting CCS values to differentiate between respective isomeric pairs using the SigmaCCS program for sodium adducts is only partially achievable.

Conclusions

ESI CID spectra of [M + Li]⁺ adduct ions for individual glycal disaccharide analogues facilitate the discrimination between alpha and beta (1-4) linked unsaturated disaccharides and their 2-C-branched analogues. Through optimized experimental conditions, complete baseline ion mobility separation of stereoisomer pairs of the Cs adducts is achieved.

理由 (1-4) 连接二糖的 1，2-不饱和衍生物是合成生物活性化合物的多功能构建模块。区分混合物中的四对立体异构体是一项具有挑战性的任务。在本研究中，使用电喷雾离子化串联质谱（ESI-MS/MS）分析了作为碱金属加合物的二糖衍生物，包括单个化合物和混合物中的离子淌度质谱（IMS）。方法采用电喷雾离子化（ESI）结合正离子模式串联质谱法（MS/MS）来区分六乙酰基/六苄基-D-内酯和六乙酰基/六苄基-D-麦芽糖及其相应的 2-C 支链丙二酸盐的锂加成离子。具有 imeX™ 功能的阱式离子迁移率光谱仪（TIMS）的高分辨率可快速识别不同金属加合物（锂、镍、铯）的单个异构体和立体异构体混合物。测量的碰撞截面 (CCS) 值与预测的 CCS 值进行了对比分析。结果糖醛二糖类似物的 [M + Li]+ 离子的 MS/MS 光谱显示出典型的交叉环和糖苷键裂解。碰撞诱导解离（CID）光谱提供了对其碎片行为的深入了解，从而可以区分 (1-4) 连接的二糖。TIMS 技术提供了可调节的离子迁移率分辨率，可对四组立体异构化合物进行适当的分离。不过，使用 SigmaCCS 程序精确预测 CCS 值以区分各自的异构体对钠加合物只能部分实现。结论单个糖醛二糖类似物的 [M + Li]+ 加合物离子的 ESI CID 光谱有助于区分α和β（1-4）连接的不饱和二糖及其 2-C 支链类似物。通过优化实验条件，实现了 Cs 加合物立体异构体对的完全基线离子迁移率分离。

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引用次数: 0

Complete resolution across the neodymium/samarium isotopic envelope with a liquid sampling-atmospheric pressure glow discharge — Orbitrap mass spectrometer 利用液体取样-大气压辉光放电-轨道阱质谱仪全面解析钕/钐同位素包络线

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-11 DOI: 10.1002/rcm.9912

Joseph V. Goodwin, Suraj Shrestha, Benjamin T. Manard, R. Kenneth Marcus

Rationale

Nd and Sm isotope ratios play an important role in geological dating and as nuclear forensic signatures; however, the overlap of the respective 144, 148, 150 Nd/Sm isobars requires prior separations to be performed before analysis on typical MS platforms. The work presented here overcomes these isobaric interferences using ultrahigh-mass resolution to alleviate interference without prior chemical separations.

Methods

A liquid sampling-atmospheric pressure glow discharge ion source was coupled to a standard, QExactive Focus Orbitrap mass spectrometer, providing a mass resolution of ~80 k. A Spectroswiss FTMS booster X2 data acquisition package was used to collect extended transients, providing much higher mass resolution; ~230 k and ~600 k are employed here for Nd and Sm isotopes.

Results

While the standard Orbitrap resolution is far greater than typical “atomic” MS platforms, it was insufficient to alleviate all isobars. The use of a resolution of ~230 k resulted in baseline separation across the entire isotopic envelope for both Nd and Sm. Isotope ratios obtained from Nd:Sm mixtures using high-resolution were equivalent to those found for individual-element solutions, while isotope ratios obtained at a resolution of ~80 k (standard for the OEM data system) showed large deviations.

Conclusions

Use of ultrahigh-resolution is an attractive alternative to extensive chemical separations to alleviate severe isobaric interferences. Sufficient mass resolution greatly reduces/eliminates the need for sample manipulations (separations) before analysis while reducing costs and total analysis times.

理由 Nd 和 Sm 同位素比在地质年代测定和核鉴识特征方面发挥着重要作用；然而，由于 144、148、150 Nd/Sm 同位素条的重叠，因此在典型的质谱平台上进行分析之前，需要事先进行分离。本文介绍的工作利用超高质量分辨率克服了这些等压干扰，无需事先进行化学分离即可减轻干扰。方法液体取样-大气压辉光放电离子源与标准 QExactive Focus Orbitrap 质谱仪相连，提供 ~80 k 的质量分辨率。Spectroswiss FTMS 助推器 X2 数据采集软件包用于采集扩展瞬态数据，提供更高的质量分辨率；这里对钕和钐同位素分别采用了 ~230 k 和 ~600 k 的分辨率。结果虽然标准 Orbitrap 分辨率远高于典型的 "原子 "质谱平台，但仍不足以消除所有等压线。使用 ~230 k 的分辨率可以对 Nd 和 Sm 的整个同位素包络线进行基线分离。使用高分辨率从 Nd:Sm 混合物中获得的同位素比值与单个元素溶液中的同位素比值相当，而使用 ~80 k 分辨率（OEM 数据系统的标准）获得的同位素比值则显示出很大的偏差。结论使用超高分辨率是一种有吸引力的替代方法，可替代广泛的化学分离来减轻严重的等压干扰。足够的质量分辨率可大大减少/消除分析前的样品处理（分离）需求，同时降低成本并缩短总分析时间。

{"title":"Complete resolution across the neodymium/samarium isotopic envelope with a liquid sampling-atmospheric pressure glow discharge — Orbitrap mass spectrometer","authors":"Joseph V. Goodwin, Suraj Shrestha, Benjamin T. Manard, R. Kenneth Marcus","doi":"10.1002/rcm.9912","DOIUrl":"https://doi.org/10.1002/rcm.9912","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Nd and Sm isotope ratios play an important role in geological dating and as nuclear forensic signatures; however, the overlap of the respective 144, 148, 150 Nd/Sm isobars requires prior separations to be performed before analysis on typical MS platforms. The work presented here overcomes these isobaric interferences using ultrahigh-mass resolution to alleviate interference without prior chemical separations.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>A liquid sampling-atmospheric pressure glow discharge ion source was coupled to a standard, QExactive Focus Orbitrap mass spectrometer, providing a mass resolution of ~80 k. A Spectroswiss FTMS booster X2 data acquisition package was used to collect extended transients, providing much higher mass resolution; ~230 k and ~600 k are employed here for Nd and Sm isotopes.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>While the standard Orbitrap resolution is far greater than typical “atomic” MS platforms, it was insufficient to alleviate all isobars. The use of a resolution of ~230 k resulted in baseline separation across the entire isotopic envelope for both Nd and Sm. Isotope ratios obtained from Nd:Sm mixtures using high-resolution were equivalent to those found for individual-element solutions, while isotope ratios obtained at a resolution of ~80 k (standard for the OEM data system) showed large deviations.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>Use of ultrahigh-resolution is an attractive alternative to extensive chemical separations to alleviate severe isobaric interferences. Sufficient mass resolution greatly reduces/eliminates the need for sample manipulations (separations) before analysis while reducing costs and total analysis times.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 23","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.9912","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142174091","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

Multireflecting gas chromatography-multireflecting time-of-flight mass spectrometer with high dynamic range 高动态范围多反射气相色谱-多反射飞行时间质谱仪

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-10 DOI: 10.1002/rcm.9909

Aleksey V. Vorobyev, Yury I. Khasin, Vasily V. Makarov, Sergey N. Kirillov, Anatoly N. Verenchikov

Gas chromatography–mass spectrometry (GC–MS) is a cornerstone technique for analyses of volatile and semivolatile compounds, constantly evolving to meet new challenges. The adoption of time-of-flight mass spectrometers (TOFMS) has enhanced GC–MS with faster spectral acquisition and broader mass coverage, enabling rapid GC separations. Multireflecting TOFMS (MRT) further improves resolution compared to traditional single-reflecting TOFMS, facilitating the detection of minor analytes within complex matrices. This paper presents a significant improvement in MRT sensitivity and dynamic range achieved through an ion beam compression within the ion guide and the use of a conventionally oriented orthogonal accelerator. Sensitivity is improved to 100 000 ion/pg at a resolution of R = 25,000, enabling the detection of low fg analyte quantities within 3 μg of matrix material into MS. The demonstrated linear dynamic range exceeding 6 orders of magnitude potentially enables even deeper exploration of complex mixtures with a bench top instrument.

气相色谱-质谱联用仪（GC-MS）是分析挥发性和半挥发性化合物的基础技术，它不断发展以应对新的挑战。飞行时间质谱仪 (TOFMS) 的采用提高了 GC-MS 的光谱采集速度和质量覆盖范围，实现了快速 GC 分离。与传统的单反射 TOFMS 相比，多反射 TOFMS（MRT）进一步提高了分辨率，有助于检测复杂基质中的微量分析物。本文介绍了通过在离子导向器内压缩离子束和使用传统的正交加速器而实现的 MRT 灵敏度和动态范围的显著提高。灵敏度提高到 100 000 个离子/pg，分辨率为 R = 25,000，从而能够在 MS 中检测到 3 μg 基质材料中的低 fg 分析物。已证实的线性动态范围超过 6 个数量级，这使得使用台式仪器对复杂混合物进行更深入的探索成为可能。

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引用次数: 0

Development of an UPLC-MS/MS approach to detect and quantify N-nitroso mirabegron in mirabegron 开发一种 UPLC-MS/MS 方法，用于检测和量化米拉贝琼中的 N-亚硝基米拉贝琼。

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2024-09-06 DOI: 10.1002/rcm.9911

Ravi Uppala, Rakesh Chandrakant Prabhu, Arthanareeswari Maruthapillai, Bandaru Venkatasubbaiah, Gopal Chandru Senadi, Sundaramurthy Devikala

In the mirabegron (MIR) synthesis, the N-nitroso mirabegron (NNM) is obtained during synthetic process of MIR; water is being used in reaction under acidic condition. Nitrite source is from water, and secondary amine source is from MIR as it has secondary amine; NNM is generated as an impurity during the synthesis of MIR. The presence of NNM in MIR could potentially affect its effectiveness. The purpose of this study was to establish a Ultra-performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC-MS/MS) methodology to identify NNM in MIR samples. The method for NNM analysis was developed on Acquity HSS T3 (100*2.1) mm 1.8 μm column with gradient elution using mobile phase consisted of 0.1% formic acid in water (mobile phase A) and 0.1% formic acid in methanol (mobile phase B). Mass spectrometer with electrospray ionization operated in the MRM mode was used in the analysis of NNM (m/ z 426.20 → 170.00). The UPLC-MS/MS methodology proposed showed a good linearity (0.02 to 0.72 ppm), good system precision (RSD = 0.57%), good method precision (RSD = 0.87%), acceptable accuracy (94.5–116.5%), low detection limit (0.006 ppm) and low quantification limit (0.02 ppm) for NNM. The UPLC-MS/MS methodology proposed can be utilized to assess the quality of MIR sample for the presence of NNM impurity.

在米拉贝琼（MIR）的合成过程中，N-亚硝基米拉贝琼（NNM）是在米拉贝琼的合成过程中获得的；水在酸性条件下用于反应。亚硝酸盐来源于水，仲胺来源于 MIR，因为 MIR 具有仲胺；NNM 是 MIR 合成过程中产生的杂质。MIR 中含有 NNM 可能会影响其功效。本研究的目的是建立一种超高效液相色谱-质谱/质谱（UPLC-MS/MS）方法，以鉴定 MIR 样品中的 NNM。NNM 分析方法采用 Acquity HSS T3 (100*2.1) mm 1.8 μm 色谱柱，以 0.1% 甲酸水溶液（流动相 A）和 0.1% 甲酸甲醇（流动相 B）为流动相进行梯度洗脱。采用电喷雾离子化质谱仪，以 MRM 模式分析 NNM（m/ z 426.20 → 170.00）。所提出的 UPLC-MS/MS 方法对 NNM 具有良好的线性（0.02 至 0.72 ppm）、良好的系统精密度（RSD = 0.57%）、良好的方法精密度（RSD = 0.87%）、可接受的准确度（94.5-116.5%）、较低的检测限（0.006 ppm）和较低的定量限（0.02 ppm）。所提出的 UPLC-MS/MS 方法可用于评估 MIR 样品中 NNM 杂质的质量。

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引用次数: 0