Rapid Communications in Mass Spectrometry最新文献_第6页

Laser Ablation Sampling With Low-Power Plasma: A LA-MIP-MS Instrument for Spaceflight 低功率等离子体激光烧蚀取样：一种用于航天的LA-MIP-MS仪器。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-24 DOI: 10.1002/rcm.10152

Benjamin J. Farcy, Jacob Graham, Madeline Raith, Ricardo Arevalo Jr., Mazdak Taghioskoui, Sierra Budinoff, Amy McAdam, Jane Lee, Ryan M. Danell, Desmond A. Kaplan, Cynthia Gundersen, William F. McDonough

Rationale

Inductively coupled plasma (ICP) is a commonly used ion source for mass spectrometry-based chemical analysis of a wide range of materials. Traditional ICP ion sources use high power (> 1000 W) and significant gas flow (> 10 L/min), rendering them unsuitable for spaceflight, as they are too resource-intensive for planetary spacecraft.

Methods

To address the technology gap, we designed and developed a laser ablation microwave-induced plasma mass spectrometer (LA-MIP-MS) and experimentally validated the analytical performance of a prototype instrument capable of providing in situ analyses during planetary science missions. We developed a low-pressure plasma ion source and interfaced it to a heritage quadrupole mass spectrometer (QMS) to perform elemental and isotopic analysis of solid samples via laser ablation. The low power plasma ion source was generated at < 1 Torr (< 133 Pa) using 30 W of power and 50 mL/min of He. Analytes were introduced via laser ablation (266 nm); we report elemental abundances and isotopic ratios for Cu, Ni, and Fe metals.

Results

Our experiments confirmed quantification accuracy for stainless steel within 1.4–4% of values measured by x-ray fluorescence (XRF), with precision ranging from ±9.1 to 22% (2σ_m). Cu and Ni isotopic ratios were measured with ±0.8–3% (2σ_m) precision and reproducibility ranging from 0.12% to 11.8%. Measured limits of detection ranged from 21 ppmw for ⁵⁷Fe to 780 ppmw for ⁵⁴Fe, with limits of detection for Cr, Mn, and Ni below 240 ppmw.

Conclusions

This technique adds to the roster of instrumentation available for planetary missions by enabling elemental and isotopic analysis with orders of magnitude less power and plasma gas relative to commercial ICP-MS systems. This work paves the way for low resource LA-MIP-MS instruments as a viable technique to be applied to a wide range of applications for terrestrial and spaceflight chemical analysis of geologic materials.

原理：电感耦合等离子体（ICP）是一种常用的离子源，用于基于质谱的多种材料的化学分析。传统的ICP离子源使用高功率（bb10 1000w）和显著的气体流量（bb10 10l /min），使得它们不适合航天飞行，因为它们对行星航天器来说过于资源密集型。方法：为了解决技术差距，我们设计并开发了激光烧蚀微波诱导等离子体质谱计（LA-MIP-MS），并通过实验验证了该原型仪器的分析性能，该仪器能够在行星科学任务中提供原位分析。我们开发了一种低压等离子体离子源，并将其连接到传统的四极杆质谱仪（QMS）上，通过激光烧蚀对固体样品进行元素和同位素分析。结果：我们的实验证实了不锈钢的定量精度在x射线荧光（XRF）测量值的1.4-4%以内，精度范围为±9.1 ~ 22% （2σm）。Cu和Ni同位素比值的测量精度为±0.8 ~ 3% (2σm)，重现性为0.12% ~ 11.8%。测定的检出限从57Fe的21 ppmw到54Fe的780 ppmw不等，Cr、Mn和Ni的检出限低于240 ppmw。结论：与商用ICP-MS系统相比，该技术使元素和同位素分析的功率和等离子体气体减少了几个数量级，从而增加了行星任务可用仪器的名单。这项工作为低资源LA-MIP-MS仪器作为一种可行的技术被广泛应用于地质材料的地面和航天化学分析铺平了道路。

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引用次数: 0

Comparison of CID and UVPD Activation to Achieve the Structural Characterization of Some Pyrolysis Bio-Oil Components. 比较CID和UVPD活化实现热解生物油组分的结构表征。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-19 DOI: 10.1002/rcm.10166

Anthony Abou Dib, Bryan Marzullo, Vincent Carré, Mark Barrow, Peter OConnor, Frédéric Aubriet

Rationale: Compounds produced by pyrolysis or hydrothermal liquefaction of lignocellulosic biomass have the potential to serve as sustainable alternatives to those derived from fossil resources. Indeed, many chemicals present in the resulting bio-oils can be utilized in the production of fuels or chemical building blocks. However, the heavy and highly oxygenated components of bio-oils require upgrading via deoxygenation or catalytic cracking. A comprehensive structural elucidation and characterization of the functional groups present in bio-oil components is essential to define the most efficient upgrading treatment, which is of importance, particularly for lignin derivatives, as some of them are resistant to upgrading processes.

Methods: Tandem mass spectrometry is a valuable tool for structural analysis. However, traditional collisional activation (CID) does not always provide sufficient information due to possible preferential fragmentation sites and patterns. Alternative activation techniques, such as ultraviolet photodissociation (UVPD), may offer additional data. The partial complementarity of UVPD and CID-MS/MS for the structural analysis of lignin-derived compounds was investigated.

Results: In this study, six lignin model compounds that efficiently absorb UV photons were investigated: 2,5-dihydroxybenzoic acid and vanillin, known to be components of pyrolysis bio-oils; coniferyl and sinapyl alcohols, two fundamental units of lignin; and two lignin dimers, pinoresinol, and guaiacylglycerol-β-guaiacylether (GGE). Collision-induced dissociation (CID) of the deprotonated standards produced by electrospray ionization, yielded characteristic fragment ions. UV activation generated additional fragment ions, some of which were valuable for determining the nature of the aromatic ring substitution.

Conclusions: Although only a small selection of compounds was examined, UVPD proved to be effective in providing additional structural information on some bio-oil components generated by lignocellulosic biomass pyrolysis. The results obtained on a Fourier transform ion cyclotron resonance mass spectrometer pave the way for two-dimensional Fourier transform mass spectrometry experiments to systematically elucidate the structures of lignin-derived compounds in bio-oils by UVPD.

原理：木质纤维素生物质热解或水热液化产生的化合物有可能成为化石资源衍生化合物的可持续替代品。实际上，生物油中存在的许多化学物质可用于生产燃料或化学构件。然而，生物油的重质和高氧成分需要通过脱氧或催化裂化来升级。对生物油成分中存在的官能团进行全面的结构解析和表征对于确定最有效的升级处理至关重要，特别是对于木质素衍生物，因为它们中的一些对升级过程具有抗性。方法：串联质谱法是一种有价值的结构分析工具。然而，传统的碰撞激活（CID）并不总是提供足够的信息，由于可能的优先破碎位点和模式。其他激活技术，如紫外线光解（UVPD），可能提供额外的数据。研究了UVPD和CID-MS/MS在木质素衍生物结构分析中的部分互补性。结果：研究了六种有效吸收紫外光子的木质素模型化合物：2,5-二羟基苯甲酸和香兰素，它们是热解生物油的主要成分；木质素的两个基本单位松柏醇和新树醇；以及两种木质素二聚体，松脂醇和愈创木酰甘油-β-愈创木酰醚（GGE）。电喷雾电离产生的去质子标准物的碰撞诱导解离（CID）产生特征碎片离子。紫外活化产生了额外的片段离子，其中一些对确定芳香环取代的性质有价值。结论：虽然只检测了一小部分化合物，但UVPD被证明可以有效地提供由木质纤维素生物质热解产生的一些生物油成分的额外结构信息。在傅里叶变换离子回旋共振质谱仪上获得的结果为二维傅里叶变换质谱实验铺平了道路，从而系统地阐明了生物油中木质素衍生化合物的结构。

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引用次数: 0

Identification and Characterisation of UV Inactive Acid Degradation Impurities of Rebaudioside A Using LC-HRMS/MS, Greenness Evaluation and In Silico Toxicity Studies 采用LC-HRMS/MS对雷鲍迪苷A的紫外无活性酸降解杂质进行鉴定、表征、绿度评价和硅毒性研究。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-19 DOI: 10.1002/rcm.10173

Muhammad Naheel, Gayatri Gajanan Kulkarni, G. SaiKrishna, Nagaraju Rajana

Rationale

Rebaudioside A is a predominant steviol glycoside, extracted from Stevia rebaudiana Bertoni leaves and is used as an alternative to sucrose in food and beverages. It undergoes degradation in various conditions, resulting in the formation of degradation products. The identification and characterisation of these degradation impurities are essential for understanding compound stability and product safety, especially the UV-inactive degradation impurities, which are not detected in UV-HPLC by previously reported methods.

Methods

A robust HPLC method was developed and validated using an XBridge BEH amide column with 10 mM ammonium acetate and acetonitrile (20:80% v/v) as the mobile phase, at 1.0 mL/min flow,10 μL injection, and 40 °C column temperature. Degradation products (DPs) formed under acid and base degradation were identified using LC-HRMS/MS. In silico ADME and toxicity profiling were performed using ProTox 3.0 and Pre ADMET. The environmental impact of the method was assessed using the AGREE tool.

Results

The method was linear over 0.10–5.0 mg/mL with LOD and LOQ of 0.025 mg/mL and 0.10 mg/mL, respectively. Five DPs were identified in acid degradation and four DPs were identified under base degradation. The DP-3 was identified as (3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl acetate, which was not reported previously. The toxicity analysis of the degradation impurities showed that the acid DPs were mostly class 4, moderately toxic, except DP-3, which was class 6 and non-toxic, and the entire base DPs were non-toxic. The AGREE tool gave the method a greenness score of 0.75, indicating strong environmental compatibility.

Conclusions

The study provides a valuable understanding of the degradation behaviour of rebaudioside A in various conditions. All the degradation products were identified, including DP-3, which was identified as(3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl acetate. Additionally, in silico toxicity and ADMET studies provided a safety profile of degradation impurities. The AGREE score of the validated method indicates that the developed method is suitable as an environmentally friendly analytical approach.

原理：甜菊糖苷A是一种主要的甜菊醇糖苷，从甜菊叶中提取，在食品和饮料中用作蔗糖的替代品。它在各种条件下发生降解，形成降解产物。这些降解杂质的鉴定和表征对于了解化合物的稳定性和产品的安全性至关重要，特别是在UV-HPLC中未被检测到的紫外线非活性降解杂质。方法：采用XBridge BEH酰胺色谱柱，流动相为10 mM乙酸铵和乙腈（20:80% v/v），流速1.0 mL/min，进样量10 μL，柱温40℃，建立高效液相色谱法。采用LC-HRMS/MS对酸碱降解形成的降解产物进行鉴定。使用ProTox 3.0和Pre ADMET进行计算机ADME和毒性分析。使用AGREE工具评估该方法的环境影响。结果：该方法在0.10 ~ 5.0 mg/mL范围内线性良好，定量限和定量限分别为0.025 mg/mL和0.10 mg/mL。在酸降解中鉴定出5个DPs，在碱降解中鉴定出4个DPs。DP-3鉴定为(3R,4S,5S,6R)-3,4,5-三羟基-6-（羟甲基）四氢- 2h -吡喃-2-乙酸酯，此前未见报道。对降解杂质的毒性分析表明，除DP-3为6级无毒外，酸性DPs大部分为4级中毒性，碱性DPs全部无毒。AGREE工具给出的绿色度评分为0.75，表明该方法具有较强的环境兼容性。结论：本研究为了解雷鲍迪苷a在不同条件下的降解行为提供了有价值的认识。对所有降解产物进行了鉴定，包括DP-3，鉴定为(3R,4S,5S,6R)-3,4,5-三羟基-6-（羟甲基）四氢- 2h -吡喃-2-乙酸酯。此外，在硅毒性和ADMET研究提供了降解杂质的安全性概况。经过验证的方法的AGREE分数表明，所开发的方法适合作为一种环境友好的分析方法。

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引用次数: 0

Identification and Structural Characterization of Degradation Products of Tivozanib Using LC-Q-TOF-MS/MS and NMR: An In Silico Approach for Degradation and Toxicity Prediction 用LC-Q-TOF-MS/MS和NMR鉴定替沃赞尼降解产物及其结构表征：一种用于降解和毒性预测的硅方法。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-17 DOI: 10.1002/rcm.10167

Nadeem Shaikh, Sowmya Chaganti, Rahul Khemchandani, Dharipally Harini, H. M. Chandra Mouli, Gananadhamu Samanthula

Rationale

The present study investigated the degradation behaviour of tivozanib (TVZ), a potent tyrosine kinase inhibitor, under various stress conditions, including hydrolytic (acid, base, and neutral), oxidative, thermal, and photolytic (UV and visible light) conditions. The resulting degradation products (DPs) were characterized by LC-Q-TOF-MS/MS and NMR. Additionally, in silico toxicity assessment and mutagenicity studies were accomplished by using DEREK Nexus and SARAH Nexus for TVZ and its DPs.

Methods

The in silico degradation profile of TVZ was predicted using Zeneth software. Separation of the DPs was executed by RP-HPLC with gradient elution mode using Shim-pack Solar C18 column (250 × 4.6 mm, 5 μm). The mobile phase consists of solvent A as 10 mM ammonium acetate buffer (pH 3.8) and solvent B as a mixture of acetonitrile:methanol (70%:30% v/v). Structural characterization was performed for TVZ and its DPs using LC-Q-TOF-MS/MS and NMR spectroscopy.

Results

TVZ was sensitive to hydrolytic (acid, base, and neutral), oxidative, and photolytic (UV light) degradation conditions, wherein seven DPs were observed and separated by RP-HPLC. A plausible degradation pathway of TVZ was proposed based on mass spectrometry data. The preparative HPLC was used to isolate DP-III, DP-IV, and DP-VI, and the structures were confirmed by NMR spectroscopy. Furthermore, the 2D NMR data helped to differentiate the chemical structure of DP-IV, which had the same molecular mass as TVZ.

Conclusion

Forced degradation studies were conducted in accordance with ICH Q1A (R2) and Q1B guidelines. Totally, seven DPs were observed in various stress conditions. DP-IV, a structural isomer of TVZ, was detected in basic hydrolytic conditions. The developed RP-HPLC method was validated following the ICH Q2(R1). This study helps in the stability testing and routine quality control analysis during the formulation development of TVZ.

基本原理：本研究调查了tivozanib (TVZ)，一种有效的酪氨酸激酶抑制剂，在各种应激条件下的降解行为，包括水解（酸，碱和中性），氧化，热和光解（紫外线和可见光）条件。通过LC-Q-TOF-MS/MS和NMR对降解产物进行了表征。此外，利用DEREK Nexus和SARAH Nexus对TVZ及其DPs进行了硅毒性评估和致突变性研究。方法：采用Zeneth软件对TVZ的硅降解曲线进行预测。色谱柱为Shim-pack Solar C18 (250 × 4.6 mm, 5 μm)，采用梯度洗脱的反相高效液相色谱分离。流动相由溶剂A作为10 mM醋酸铵缓冲液（pH 3.8）和溶剂B作为乙腈：甲醇的混合物（70%:30% v/v）组成。采用LC-Q-TOF-MS/MS和NMR对TVZ及其DPs进行了结构表征。结果：TVZ对水解（酸、碱、中性）、氧化、光解（紫外光）降解条件敏感，其中7种DPs通过RP-HPLC进行了观察和分离。基于质谱分析，提出了一种合理的TVZ降解途径。采用制备高效液相色谱法分离DP-III、DP-IV和DP-VI，并通过NMR对其结构进行了确证。此外，二维NMR数据有助于区分DP-IV的化学结构，DP-IV与TVZ具有相同的分子质量。结论：根据ICH Q1A （R2）和Q1B指南进行了强制降解研究。在不同的胁迫条件下，共观察到7种DPs。在碱性水解条件下检测到TVZ的结构异构体DP-IV。建立的反相高效液相色谱法按照ICH Q2（R1）进行验证。本研究为tvb配方开发过程中的稳定性测试和常规质量控制分析提供了依据。

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引用次数: 0

Optimization and Application of Automatic Cryogenic Vacuum Distillation System for Fruit Water Extraction for Isotope Analysis 果水萃取同位素分析用低温真空自动蒸馏系统的优化与应用

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-17 DOI: 10.1002/rcm.10175

Lianrong He, Yanjun Ju, Hongjie Qiao, Jie Zhao, Meng Wang, Duoyong Zhao, An Li

Stable hydrogen (δ²H) and oxygen (δ¹⁸O) isotopes in plant tissue water provide effective indicators for tracing fruit origin. This study optimized automatic cryogenic vacuum distillation (ACVD) system parameters (temperature, extraction time, and sample volume) to achieve a near-complete water recovery and high analytical accuracy. Systematic deviations of isotopic values between the original water and the water extracted from the spiked strawberry samples (Δδ²H: 4.56‰; Δδ¹⁸O: 1.14‰) were observed, likely due to matrix effects during extraction. Nevertheless, the optimized ACVD protocol enabled clear discrimination of the geographical origins of strawberries, apples, and kiwifruits based on their δ²H and δ¹⁸O values. These results indicate that, despite extraction-induced isotopic fractionation, tissue water isotopes remain reliable markers for fruit provenance when ACVD parameters are carefully controlled.

植物组织水中稳定的氢（δ2H）和氧（δ18O）同位素为果实溯源提供了有效的指标。本研究优化了自动低温真空蒸馏（ACVD）系统参数（温度、萃取时间和样品体积），实现了近乎完全的水回收率和高分析精度。原水与加峰草莓样品中提取的水之间的同位素值存在系统偏差（Δδ2H: 4.56‰；Δδ18O: 1.14‰），这可能是由于提取过程中的基质效应所致。然而，优化后的ACVD方案可以根据草莓、苹果和猕猴桃的δ2H和δ18O值对其地理来源进行清晰的区分。这些结果表明，尽管提取引起了同位素分馏，但当ACVD参数得到严格控制时，组织水同位素仍然是水果来源的可靠标记。

引用次数: 0

Enhancing Chimeric Fragmentation Spectra Deconvolution Using Direct Infusion–Tandem Mass Spectrometry Across High-Resolution Mass Spectrometric Platforms 在高分辨率质谱平台上使用直接输注串联质谱增强嵌合碎片谱反褶积。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-16 DOI: 10.1002/rcm.10170

Arina Ivanova, Wei Tang, Carsten Simon, Kai Dührkop, Sebastian Böcker, Gerd Gleixner

Rationale

Direct infusion mass spectrometry (DI-MS) is a rapid analytical technique widely used in omics research and other fields. However, the complexity of DI-MS spectra frequently leads to co-fragmentation of analytes with similar m/z, resulting in chimeric fragmentation spectra that complicate compound identification. A DI-based tandem mass spectrometric method (DI-MS2), which modulates the intensity of precursors and fragments by the stepwise movement of the quadrupole isolation window, has been shown to successfully deconvolute chimeric fragmentation spectra. Yet, its applicability to different instruments and optimisation has not been evaluated.

Method

We evaluate the performance of DI-MS2 on two high-resolution instruments: a linear ion trap-Orbitrap (LIT-Orbitrap) and a quadrupole-Orbitrap (Q-Orbitrap). We examined the impact of six instrumental settings, including mass resolving power, isolation window width, step size between MS2 scans, number of microscans, collision energy and automatic gain control (AGC) target, on the analysis of isobaric mixtures with varying m/z differences.

Results

The LIT-Orbitrap consistently achieved high-quality chimeric spectra deconvolution with an average similarity score of 0.98 despite unexpected intensity modulation patterns. The Q-Orbitrap provided four times faster measurements but showed more variable results: It achieved a similarity score of 0.96 for isobars with a m/z difference larger than 0.02, but only 0.56 for m/z differences of 0.006.

Conclusions

These findings indicate that the DI-MS2 is a robust and flexible method applicable across different MS platforms, though the Q-Orbitrap may be less suited for highly complex samples with multiple peaks per nominal mass. This highlights the potential of the DI-MS2 for structural elucidation of complex biological mixtures. Additionally, we provide initial setting optimisation guidelines to improve spectra deconvolution and measurement speed.

原理：直接输注质谱（Direct infusion mass spectrometry, DI-MS）是一种广泛应用于组学研究等领域的快速分析技术。然而，由于DI-MS谱的复杂性，往往导致具有相似m/z的分析物共破碎，从而产生嵌合破碎谱，使化合物鉴定复杂化。基于di的串联质谱方法（DI-MS2）通过四极隔离窗口的逐步移动来调节前体和碎片的强度，已被证明可以成功地反褶曲嵌合碎片谱。然而，它对不同仪器和优化的适用性尚未得到评估。方法：在线性离子阱-轨道阱（lite - orbitrap）和四极离子阱-轨道阱（Q-Orbitrap）两种高分辨率仪器上评价DI-MS2的性能。我们研究了六种仪器设置，包括质量分辨率、隔离窗宽度、MS2扫描之间的步长、微扫描次数、碰撞能量和自动增益控制（AGC）目标，对具有不同m/z差的等压混合物分析的影响。结果：尽管存在意想不到的强度调制模式，lit_orbitrap仍能获得高质量的嵌合光谱反褶积，平均相似度得分为0.98。Q-Orbitrap提供了四倍快的测量速度，但显示了更多可变的结果：对于m/z差大于0.02的等压线，它的相似性得分为0.96，但对于m/z差为0.006的等压线，它的相似性得分仅为0.56。结论：这些发现表明，DI-MS2是一种稳健且灵活的方法，适用于不同的质谱平台，尽管Q-Orbitrap可能不太适合具有每标称质量多个峰的高度复杂样品。这突出了DI-MS2在复杂生物混合物结构解析方面的潜力。此外，我们还提供了初始设置优化指南，以提高光谱反褶积和测量速度。

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引用次数: 0

Editorial-In Memory of Jean-François Muller. 社论-纪念让-弗朗索瓦·穆勒。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-09 DOI: 10.1002/rcm.10168

Laurence Charles, Frédéric Aubriet

引用次数: 0

Direct Identification and Quantification of Flavonoids and Their Structural Isomers Using Ambient Ionization Tandem Mass Spectrometry 环境电离串联质谱法直接鉴定和定量黄酮类化合物及其结构异构体

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-11-08 DOI: 10.1002/rcm.10169

Yanqiu Wang, Liping Xu, Tiange Gu, Hongli Li, David Da Yong Chen

Rationale

Flavonoids are phenolic compounds with many health-benefiting properties. However, differentiating different types of flavonoids and their isomers is challenging due to their highly similar structures of various subtypes and different numbers and sites of substituents. Timely quality evaluation of flavonoid-based products is currently almost impossible.

Methods

An ambient ionization method of direct analysis in real time (DART) ion source and tandem mass spectrometry (MS) was used to characterize the fine structures of flavonoids. Different flavonoid subtypes and their isomers with varied numbers and sites of substituents were subjected to DART ionization and collision-induced fragmentation MS analysis.

Results

Seven classes of flavonoids, including methoxy-substituted compounds, exhibited distinctive fragmentation pathways such as retro-Diels-Alder reactions, cross-ring cleavages, and neutral losses. Many flavonoid isomers produced diagnostic MS² and MS³ fragments through DART-tandem MS, enabling direct identification of various isomers within mixtures. An identification workflow was developed, culminating in the creation of a computational tool called FlavoFinder, which automatically determines flavonoid aglycone subtypes and their isomeric structures.

Conclusions

The method and the structural elucidation program were successfully used for the qualitative and quantitative analysis of different flavonoid isomers from real samples. The analysis procedure is high-throughput and is capable of characterizing complex flavonoid structures without extensive sample pretreatment and front-end chromatographic separations.

黄酮类化合物是酚类化合物，具有许多有益健康的特性。然而，由于不同类型的类黄酮及其异构体的结构高度相似，取代基的数量和位置也不同，因此区分不同类型的类黄酮及其异构体具有挑战性。目前，对类黄酮类产品进行及时的质量评价几乎是不可能的。方法采用环境电离实时直接分析（DART）离子源法和串联质谱法（MS）对黄酮类化合物的精细结构进行表征。不同的类黄酮亚型及其不同取代基数量和位置的异构体进行DART电离和碰撞诱导碎片质谱分析。结果7类黄酮类化合物，包括甲氧基取代化合物，均表现出不同的裂解途径，如逆diols - alder反应、交叉环裂解和中性损失。许多类黄酮异构体通过dart串联质谱产生诊断MS2和MS3片段，从而可以直接鉴定混合物中的各种异构体。开发了一个鉴定工作流程，最终创建了一个名为FlavoFinder的计算工具，该工具可以自动确定类黄酮苷元亚型及其异构体结构。结论该方法和结构解析程序可用于实际样品中不同类黄酮异构体的定性和定量分析。该分析方法具有高通量，能够表征复杂的类黄酮结构，而无需大量的样品前处理和前端色谱分离。

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引用次数: 0

Integration of Multiple Mass Spectrometry Techniques and Molecular Network Analysis With Bioinformatics Approaches Revealed the Mechanism of Jiuwei Xifeng Granules in the Treatment of Tourette's Syndrome 多重质谱技术和分子网络分析结合生物信息学方法揭示九味西风颗粒治疗抽动秽语综合征的机制。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-10-30 DOI: 10.1002/rcm.10156

Chenning Zhang, Pengfei Zhao, Limin Xing, Ruiqi Zhu, Zhiyan Liu, Ying Li, Shuang Li, Chun Bao, Mo Sun, Zhenzhong Wang, Wei Xiao

Rationale

Jiuwei Xifeng Granules, a Chinese patent medicine developed based on renowned traditional Chinese medicine, has shown significant clinical efficacy in treating Tourette's syndrome. However, there is limited research on its pharmacological compounds and mechanism of action.

Methods

In this study, high-resolution mass spectrometry (HRMS) was employed to analyze the natural organic small molecules in the herbal ingredients of Jiuwei Xifeng Granules and the drug-derived components in the serum, liver, and brain tissues of mice following long-term administration, as well as the protein components in the animal drugs. Meanwhile, inorganic trace elements are also widely assessed in Jiuwei Xifeng Granules. Molecular network analysis is utilized to further analyze the natural organic small molecules. Finally, network pharmacology and molecular docking techniques were employed to investigate the mechanisms of action of the main active ingredients.

Results

In total, 51 natural organic small molecules were identified in the five herbal medicines of Jiuwei Xifeng Granules, and the main active components included Gastrodin, Gentiopicroside, and Geissoschizine methyl ether. A total of 22 drug-derived components were identified in the blood of mice, 18 components were detected in the liver, and 8 were found in the brain tissue. Molecular network analysis further expanded the range of identified natural small molecule organic compounds. Thirty-six proteins were identified from two animal drugs in Jiuwei Xifeng Granules, and 68 trace elements were identified from two mineral medicines in Jiuwei Xifeng Granules. The results of the systems pharmacology analysis confirm that the pharmacological action pathways include serotonergic synapse, neuroactive ligand-receptor interaction, dopaminergic synapse, and cAMP signaling pathway. The main targets included DRD2, SLC6A4, HTR1A, DRD1, and KCNH2.

Conclusion

This study employed a multi-omics approach to comprehensively analyze the active compounds in Jiuwei Xifeng Granules, providing a chemical foundation for elucidating its mechanism of action in treating Tourette's syndrome.

理由：九味西风颗粒是一种以著名中医为基础研制的中成药，对治疗抽动秽语综合征具有显著的临床疗效。然而，对其药理成分和作用机制的研究有限。方法：采用高分辨率质谱法（HRMS）分析九味西风颗粒中草药成分中的天然有机小分子，长期给药小鼠血清、肝脏、脑组织中的药源性成分，以及动物性药物中的蛋白质成分。同时，九味西风颗粒中无机微量元素也得到了广泛的评价。利用分子网络分析法对天然有机小分子进行进一步分析。最后，利用网络药理学和分子对接技术对其主要活性成分的作用机制进行了研究。结果：九味西风颗粒中共鉴定出51种天然有机小分子，主要有效成分为天麻素、龙胆苦苷、葛缕荆甲醚。在小鼠血液中共鉴定出22种药物源性成分，在肝脏中检测到18种成分，在脑组织中发现8种成分。分子网络分析进一步扩大了天然小分子有机化合物的鉴定范围。从九味西风颗粒中分离出2种动物药物36种蛋白质，从九味西风颗粒中分离出2种矿物药物68种微量元素。系统药理学分析结果证实其药理作用途径包括5 -羟色胺能突触、神经活性配体-受体相互作用、多巴胺能突触和cAMP信号通路。主要靶点包括DRD2、SLC6A4、HTR1A、DRD1和KCNH2。结论：本研究采用多组学方法综合分析九味西风颗粒的活性成分，为阐明其治疗抽动秽语综合征的作用机制提供化学基础。

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引用次数: 0

Differentiation of α2–3- and α2–6-Linked Sialic Acid Linkages Using Esterification/Amidation Reactions and Tandem Mass Spectrometry 用酯化/酰胺化反应和串联质谱技术鉴别α2-3 -和α2 - 6-唾液酸键

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-10-29 DOI: 10.1002/rcm.10165

Wei-Chien Weng, Hsien-Wei Tseng, Chin-Yu Liang, Hsin-Kai Tseng, Ching-Ching Yu, Chun-Cheng Lin, Chi-Kung Ni

Rational

Among various oligosaccharides, sialylated oligosaccharides play crucial roles in both physiological and pathological processes, and sialic acid residues within these structures are often used as biomarkers. Mass spectrometry is a widely utilized tool for glycan structural analysis. However, sialic acid is prone to elimination during the sample preparation and the activation process in tandem mass spectra, resulting in a loss of information on sialylation. Consequently, the identification of sialic acid linkages presents a significant analytical challenge. One established method for differentiating α2 → 3- and α2 → 6-linked sialic acids involves esterification followed by ammonia treatment. In this process, the carboxyl group of α2 → 3-linked sialic acids is converted into an amide, while α2 → 6-linked sialic acids are transformed into esters, resulting in distinguishable molecular weights. However, partial conversion of α2 → 6-linked sialic acids to amides and α2 → 3-linked sialic acids to esters has been observed, which reduces the reliability of this differentiation approach.

Methods

A simple tandem mass spectrometry, based on the dissociation mechanisms of hexose and N-acetylhexosamine, is proposed to differentiate α2 → 3 and α2 → 6 sialic acid linkages after esterification and amidation.

Results

Various oligosaccharides consisting of sialic acid with α2 → 3 or α2 → 6 linkages were studied. For some oligosaccharides, the amidation for α2 → 3 linked sialic acid and esterification for α2 → 6 linked sialic acid are nearly complete, while partial amidation for α2 → 6 linked sialic acid and partial esterification for α2 → 3 linked sialic acid for other oligosaccharides was found, suggesting differentiation cannot be solely dependent on the amidation and esterification (or molecular weights). We showed that the α2 → 3 and α2 → 6 linked sialic acids after esterification/amidation can be distinguished by a simple tandem mass spectrometry.

Conclusions

The proposed tandem mass spectrometry enables accurate differentiation of α2 → 3 and α2 → 6 sialic acid linkages, even when both of them undergo amidation or esterification.

在各种寡糖中，唾液酸寡糖在生理和病理过程中都起着至关重要的作用，唾液酸残基在这些结构中经常被用作生物标志物。质谱法是一种广泛应用于多糖结构分析的工具。然而，在串联质谱中，唾液酸在样品制备和激活过程中容易被消除，导致唾液化信息的丢失。因此，唾液酸连接的鉴定提出了一个重大的分析挑战。已建立的区分α2→3-和α2→6-链唾液酸的方法包括酯化反应和氨处理。在此过程中，α2→3链唾液酸的羧基转化为酰胺，α2→6链唾液酸的羧基转化为酯，从而产生可区分的分子量。然而，α2→6链唾液酸部分转化为酰胺，α2→3链唾液酸部分转化为酯，这降低了这种分化方法的可靠性。方法基于己糖和n -乙酰己糖胺的解离机制，采用简单的串联质谱法对α2→3键和α2→6键在酯化和酰胺化后进行区分。结果研究了由α2→3或α2→6键的唾液酸组成的各种低聚糖。对于某些低聚糖，α2→3连接唾液酸的酰胺化和α2→6连接唾液酸的酯化反应基本完成，而对于其他低聚糖，α2→6连接唾液酸的部分酰胺化和α2→3连接唾液酸的部分酯化反应基本完成，提示分化不能仅仅依赖于酰胺化和酯化反应（或分子量）。结果表明，经过酯化/酰胺化反应的α2→3和α2→6链唾液酸可以用简单的串联质谱法进行区分。结论所建立的串联质谱法能够准确区分α2→3和α2→6唾液酸键，即使它们都发生了酰胺化或酯化反应。

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引用次数: 0