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

Fluorination of Silver Phosphate in Nickel Reaction Vessels for Triple Oxygen Isotope Analysis 三氧同位素分析中镍反应容器中磷酸银的氟化

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2026-01-15 DOI: 10.1002/rcm.70016

Jordan A. G. Wostbrock, Drake Yarian, Isabella Chiaravalloti, Spencer R. Moller, Ruth E. Blake

Rationale

Increasingly, more laboratories are measuring the triple oxygen isotope values of phosphate. Standardization is key to having good interlaboratory results. Here, we present the triple oxygen isotope values of a suite of standards using fluorination and compare them with previously reported triple oxygen isotope values.

Methods

Silver phosphate (~2–3 mg) was fluorinated in nickel reaction vessels, and the resulting O₂ was analyzed on a Thermo MAT 253 for the paired δ¹⁷O-δ¹⁸O value (Δ′¹⁷O). Although the δ¹⁸O and δ¹⁷O values were variable, the fluorination reaction progresses along a slope of ~0.528, indicating that the Δ′¹⁷O is constant when calculated using a λ_ref = 0.528. The ¹⁸O/¹⁶O ratio was obtained using a TC/EA, and the δ¹⁷O value was corrected based on the measured Δ′¹⁷O value from fluorination and the δ¹⁸O values obtained on the TC/EA.

Results

We provide δ¹⁷O, δ¹⁸O, and Δ′¹⁷O values for the following silver phosphate standards: NBS120c, USGS80, USGS81, AGLox, and B2207. Two new standards are also reported and available for distribution. To report our values on the VSMOW2-SLAP2 scale, we measured common silicate standards: San Carlos Olivine, NBS28, NMQ, and SKFS that have been calibrated to VSMOW2-SLAP2. Our reported Δ′¹⁷O error for silver phosphate is 10 per meg, calculated using the average long-term standard deviation of our two most replicated standards.

Conclusions

We report the δ¹⁷O, δ¹⁸O, and Δ′¹⁷O values for a large suite of silver phosphate standards and present two new standards that can be used for interlaboratory calibration. Our results are reported on the VSMOW2-SLAP2 scale by measuring silicates on the same instrument with the same reference gas. The fluorination method in nickel reaction vessels is easily adapted to other laboratories that have fluorination lines. Only 2–3 mg of silver phosphate is needed for Δ′¹⁷O measurements when paired with δ¹⁸O values using the TC-EA technique.

越来越多的实验室开始测量磷酸盐的三氧同位素值。标准化是获得良好实验室间结果的关键。在这里，我们提出了一套使用氟化的标准的三氧同位素值，并将它们与以前报道的三氧同位素值进行比较。方法在镍反应容器中氟化磷酸银（~2 ~ 3 mg），用Thermo MAT 253对生成的O2进行配对Δ 17O-δ18O值（Δ’17O）分析。虽然Δ 18o和Δ 17O值是可变的，但氟化反应沿~0.528的斜率进行，这表明当λref = 0.528时，Δ ' 17O是恒定的。18O/16O比值通过TC/EA得到，Δ 17O值根据氟化测定的Δ ' 17O值和TC/EA得到的Δ 18O值进行校正。我们提供了以下磷酸银标准品：NBS120c、USGS80、USGS81、AGLox和B2207的Δ 17O、Δ 18o和Δ ' 17O值。还报告了两个新标准，可供分发。为了报告我们在VSMOW2-SLAP2尺度上的值，我们测量了常见的硅酸盐标准：San Carlos Olivine， NBS28， NMQ和SKFS，这些标准已被校准为VSMOW2-SLAP2。我们报告的Δ ' 17O磷酸银误差为10 / meg，使用我们两个最重复标准的平均长期标准偏差计算。我们报告了大量磷酸银标准品的Δ 17O、Δ 18o和Δ ' 17O值，并提出了两种可用于实验室间校准的新标准品。我们在VSMOW2-SLAP2标度上用相同的仪器和相同的参考气体测量硅酸盐，报道了我们的结果。镍反应容器中的氟化方法很容易适用于其他有氟化线的实验室。当使用TC-EA技术与Δ 18o值配对时，仅需要2-3 mg磷酸银用于Δ ' 17O测量。

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引用次数: 0

Methodological Advances in GC–MS for Complex Plant Matrices: Profiling Essential Oils From Apiaceae Flora 复杂植物基质的气相色谱-质谱分析方法研究进展：分析蜂科植物精油。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2026-01-15 DOI: 10.1002/rcm.70029

Naiba Mehdiyeva, Nigar Mursal, Muhammad Zafar, Salman Majeed, Modhi O. Alotaibi, Khuzin Dinislam, Murodjon Yaxshimuratov, Mukhayya Ruzieva, Hami Halima, Enkelejda Kucaj

Rationale

Charmatography based pphytochemical extraction to identify and quantification of volatile bioactive compounds providing chemical profiling to evaluate their pharmacological significance.

Methods

The component composition of essential oils of Bilacunaria microcarpa (M. Bieb.) Pimenov & V.N.Tikhom. and Peucedanum ruthenicum M. Bieb. distributed in the flora of Azerbaijan was studied using the method of gas chromatography–mass spectroscopy.

Results

In the composition of the essential oil of B. microcarpa, 70 components were found, of which 59 were identified; the mains of them are beta-phellandrene (12.86%), beta-pinene (10.18%), O-cymol (8.84%), L-borneol (7.85%), 1R-alpha-pinene (7.64%), caryophyllene (7.37%), beta-caryophyllene oxide (4.43%), and β-elemene (3.97%). In the essential oil of P. ruthenicum that were also identified, 60 of them were major components, of which are m-cymene (14.08%), beta-myrcene (13.34%), limonene (9.01%), 2-methylenebornane (6.68%), acetylcyclopentanone (4.39%), 1R-alpha-pinene (3.90%), and cryptone (3.77%). Antifungal activity of both B. microcarpa and P. ruthenicum species, as well as their aqueous extracts and essential oils, was revealed.

Conclusions

It was found that the studied plants and their aqueous extracts exhibit fungistatic activity on the growth of Trichoderma lignorum and Aspergillus niger fungal colonies, whereas B. microcarpa and their aqueous extracts exhibit fungicidal action on Fusarium oxysporum, and essential oils of the studied species in all concentrations exhibited absolute fungicidal action against this fungus, Aspergillus niger.

原理：基于色谱法的植物化学提取鉴定和定量挥发性生物活性化合物，提供化学分析以评估其药理意义。方法：对小檗挥发油的成分组成进行研究。皮门诺夫和v.n.蒂洪。和鲁塞杜鹃M. Bieb。采用气相色谱-质谱联用方法研究了阿塞拜疆植物区系中分布的一种黄芪。结果：小檗挥发油成分中共检出70种成分，鉴定出59种；主要成分为-茶树烯（12.86%）、-蒎烯（10.18%）、O-cymol（8.84%）、l -冰片（7.85%）、1r - -蒎烯（7.64%）、石竹烯（7.37%）、-石竹烯氧化物（4.43%）和β-榄香烯（3.97%）。其中主要成分为间伞花烯（14.08%）、-月桂烯（13.34%）、柠檬烯（9.01%）、2-亚甲胎烯（6.68%）、乙酰环戊酮（4.39%）、1r - α -蒎烯（3.90%）和隐酮（3.77%）。结果表明，两种植物及其水提取物和精油均具有抗真菌活性。结论：所研究的植物及其水提物对木木霉和黑曲霉真菌菌落的生长具有抑制活性，而微卡柏及其水提物对尖孢镰刀菌有杀真菌作用，所研究的植物精油在所有浓度下对黑曲霉都有绝对的杀真菌作用。

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引用次数: 0

Petroleomic by Mass Spectrometry of Geochemical Biomarkers of Polar and Nonvolatile Crude Oil Fractions: Fourier Transform Ion Cyclotron Resonance Versus High-Field Orbitrap 极性和非挥发性原油馏分地球化学生物标志物的质谱分析：傅里叶变换离子回旋共振与高场轨道阱。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2026-01-05 DOI: 10.1002/rcm.70024

Luan Felipe Campos Oliveira, Jose Javier Melendez-Perez, Sérgio Eduardo Bernardo Mistura Lutzer, Alessandra Sussulini, Marcos Nogueira Eberlin

Rationale

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the gold standard in MS petroleomics due to its ultrahigh resolution and mass accuracy. But its high acquisition and maintenance costs limit accessibility. High-field Orbitrap (HFO) mass spectrometry is emerging as a promising alternative, but further evaluation is needed to determine its effectiveness in key analytical challenges of petroleomics, such as the molecular characterization of crude oils from different geological origins.

Methods

Ten crude oil samples from the Brazilian pre-salt region (five each of marine and lacustrine origin from two distinct sedimentary basins) were analyzed using ESI(−) FT-ICR MS and ESI(−) HFO MS (resolution: 840 000 at m/z 400). Molecular formula assignments were classified into heteroatom groups (NSO), and the data were interpreted using box plots, DBE vs. carbon number diagrams, and principal component analysis.

Results

HFO assigned ca. 2500 molecular formulae, compared to ca. 4500 assigned by FT-ICR. Despite this 45% lower performance, HFO preserved the overall profile of the major heteroatom classes. Notably, S₁O₄-containing compounds, which are critical markers, were identified at higher abundances with HFO, whereas marine and lacustrine oils were successfully discriminated based on NSO profiles, DBE, and carbon number. Marine oils exhibited higher oxygen content, DBE, and carbon number, whereas lacustrine oils showed relatively higher nitrogen content.

Conclusions

Despite reduced performance in formula assignments as compared to FT-ICR, HFO successfully distinguished crude oils of different geochemical origins. The present results indicate therefore that HFO, although displaying inferior performance than FT-ICR, particularly above m/z 400, still displays good enough mass resolution and accuracy sufficient to provide high quality petroleomic data normally required in most, if not all, common MS petroleomic investigations.

原理：傅里叶变换离子回旋共振质谱（FT-ICR MS）因其超高分辨率和质量精度而成为质谱石油组学的黄金标准。但其高昂的获取和维护成本限制了可访问性。高场轨道阱（High-field Orbitrap， HFO）质谱法是一种很有前景的替代方法，但需要进一步评估其在石油组学关键分析挑战中的有效性，例如不同地质来源原油的分子表征。方法：采用ESI(-) FT-ICR质谱和ESI(-) HFO质谱（分辨率：84万，m/z 400）对巴西盐下区10份原油样品（海相和湖相各5份）进行分析。分子式分配被划分为杂原子基团（NSO），数据使用箱形图、DBE与碳数图和主成分分析进行解释。结果：HFO分配了约2500个分子式，而FT-ICR分配了约4500个分子式。尽管性能降低了45%，但HFO保留了主要杂原子类的总体特征。值得注意的是，含s104的化合物是关键的标记物，用HFO鉴定出了更高的丰度，而根据NSO剖面、DBE和碳数成功地区分了海相和湖相油。海相油表现出较高的氧含量、DBE和碳数，而湖相油表现出较高的氮含量。结论：尽管与FT-ICR相比，HFO在公式赋值方面的性能有所降低，但它成功地区分了不同地球化学来源的原油。因此，目前的结果表明，HFO虽然表现不如FT-ICR，特别是在m/z 400以上，但仍然具有足够的质量分辨率和精度，足以提供大多数（如果不是全部的话）常见质谱石油勘探通常需要的高质量石油数据。

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引用次数: 0

Investigation of In-Trap High-Energy Collision Dissociation Methodology and Dissociation Conditions Using Dual-Pressure Linear Ion Trap Mass Spectrometry 利用双压力线性离子阱质谱法研究高能碰撞解离方法和解离条件。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2026-01-05 DOI: 10.1002/rcm.70025

Heyi Xu, You Jiang, Jie Xie, Li Yao, Xiang Fang, Meiying Liu, Ziyu Qu, Guang Yang, Di Zhang

Rationale

Dissociation is a critical analytical method in mass spectrometry research. Among various dissociation techniques, higher energy collision dissociation (HCD) stands out as a pivotal tool due to its ability to generate more low-mass fragment ions and directly perform dissociation during mass spectrometric detection. However, existing HCD implementations rely on specialized instrument configurations, such as collision cell structures or triple quadrupole mass spectrometers, which inevitably increase instrument development costs and technical complexity. To address this limitation, this study proposes an HCD method based on dual-pressure linear ion trap mass spectrometry that requires no additional hardware modifications.

Methods

Instead, it achieves HCD solely by optimizing the instrument's gas flow system and control parameters. By employing a nitrogen-helium gas mixture as the collision gas and testing with a reserpine standard sample, optimal dissociation conditions were obtained through adjustments to the gas mixture ratio and ion trap DC offset voltage settings.

Results

This approach successfully realizes in-trap HCD directly within the dual-pressure linear ion trap, eliminating the need for a dedicated collision cell. Furthermore, it enables HCD-based MS3 functionality, a capability unavailable in traditional triple quadrupole systems.

Conclusions

Validation experiments using veterinary drug residues fenoterol and ractopamine demonstrated the method's universality by comparing its dissociation results with those from conventional ion trap collision-induced dissociation (CID) and triple quadrupole method. The findings confirm that this strategy can be extended to other ion trap mass spectrometry platforms, offering broader applicability.

原理：解离是质谱研究中的一种关键分析方法。在各种解离技术中，高能碰撞解离（HCD）由于能够产生更多的低质量碎片离子并在质谱检测中直接进行解离而成为一种关键工具。然而，现有的HCD实现依赖于专门的仪器配置，如碰撞单元结构或三重四极杆质谱仪，这不可避免地增加了仪器开发成本和技术复杂性。为了解决这一限制，本研究提出了一种基于双压线性离子阱质谱的HCD方法，不需要额外的硬件修改。方法：单纯通过优化仪器的气流系统和控制参数来实现HCD。以氮气-氦气混合气体为碰撞气体，以利血平标准样品进行测试，通过调整气体混合比和离子阱直流偏置电压设置，获得最佳解离条件。结果：该方法成功地在双压线性离子阱中直接实现了阱内HCD，消除了对专用碰撞池的需要。此外，它还支持基于hcd的MS3功能，这是传统三重四极杆系统无法实现的功能。结论：利用兽药残留非诺特罗和莱克多巴胺进行验证实验，与传统离子阱碰撞诱导解离（CID）法和三重四极杆法的解离结果进行比较，证明了该方法的普遍性。研究结果证实，该策略可以扩展到其他离子阱质谱平台，提供更广泛的适用性。

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引用次数: 0

Determination of 15 Restricted Substances in Plastic-Packaged Food by Gas Chromatography–Mass Spectrometry 气相色谱-质谱法测定塑料包装食品中15种限制物质。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-30 DOI: 10.1002/rcm.70023

Xin Yang, Hanning Zhang, Jinqiang Yan, Hongmei Xue, Hongmei Shi, Junjie Miao

Rationale

Chemicals migrating from plastic and take-out food packaging can leach into food, posing inherent health risks to consumers. Given the ubiquitous use of plastic packaging in daily diets, reliable analytical methods for detecting restricted substances in food contact materials are imperative for safeguarding public health.

Methods

A novel analytical method, coupling gas chromatography–mass spectrometry (GC–MS) with liquid–liquid extraction for sample pretreatment, was established for the simultaneous separation and quantification of 15 common restricted substances (10 plasticizers, 1 antioxidant, and 4 ultraviolet absorbers) migrating from food plastic packaging materials into food products.

Results

The method exhibited excellent linearity (correlation coefficients, r > 0.99) across wide concentration ranges, with limits of detection (LODs) ranging from 0.005 to 0.046 mg/L. Validation data showed average recoveries of 72.30%–109.03% and relative standard deviations (RSDs, n = 6) of 1.13%–26.50%, confirming its analytical reliability.

Conclusions

This method enables rapid and accurate determination of the 15 target restricted substances, facilitating migration monitoring in food plastic packaging and strengthening technical support for food safety assessment in daily and take-out food contexts.

理由：从塑料和外卖食品包装中迁移出来的化学物质会渗入食品，对消费者构成固有的健康风险。鉴于日常饮食中普遍使用塑料包装，检测食品接触材料中受限制物质的可靠分析方法对于保障公众健康至关重要。方法：建立气相色谱-质谱联用-液液萃取前处理的分析方法，同时分离定量食品塑料包装材料中迁移到食品中的15种常见限制物质（增塑剂10种、抗氧化剂1种、紫外线吸收剂4种）。结果：该方法在较宽的浓度范围内具有良好的线性关系（相关系数为0.99），检出限为0.005 ~ 0.046 mg/L。验证数据显示，平均加样回收率为72.30% ~ 109.03%，相对标准偏差（rsd, n = 6）为1.13% ~ 26.50%，验证了该方法的分析信度。结论：该方法能够快速、准确地检测出15种目标限用物质，为食品塑料包装中的迁移监测提供了便利，为日常食品和外卖食品安全评价提供了技术支持。

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引用次数: 0

Stable Carbon and Oxygen Isotope Analysis of Carbonates and DIC Using the Delta Ray Isotope Ratio Infrared Spectrometer (IRIS): Precise and Accurate Measurements Applying a 3-Point Calibration and Standard Bracketing 使用δ射线同位素比红外光谱仪（IRIS）对碳酸盐和DIC的稳定碳氧同位素分析：精确和准确的测量应用三点校准和标准支架。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-12-29 DOI: 10.1002/rcm.70021

Maximilian Hansen, Jakob Brettschneider, Hubert Vonhof, Denis Scholz

Rationale

The Delta Ray Isotope Ratio Infrared Spectrometer enables to determine δ¹³C and δ¹⁸O values of CO₂. The measurements are calibrated against internal reference gas standards. For discrete carbonate or dissolved inorganic carbon (DIC) samples, the manufacturer recommends a calibration against two isotopically different carbonate standard materials (i.e., a 2-point calibration). Here, we show that this method is not sufficient because the measured values may drift significantly over the duration of a measurement run (i.e., 58 samples in approximately 24 h).

Methods

We developed a new measurement routine applying a 3-point calibration and a tight standard-bracketing. In addition, we present an R code to automatically evaluate and calibrate the measured data.

Results

Our standard-bracketing technique can effectively correct drifts of more than 1‰ not accounted for by the internally calibrated data. A 3-point calibration with four samples bracketed by two sets of standards provides the highest precision and accuracy, that is, the highest reproducibility for our carbonate samples. The third standard stabilizes the calibration curve and enables to better identify individual outliers.

Conclusions

Our standard-bracketing method enables accurate and precise (< 0.1‰) measurements of δ¹³C and δ¹⁸O values of calcite and DIC using the Delta Ray IRIS over a large range of values (ranging from approximately −37‰ to +2‰ in δ¹³C and from approximately −25‰ to −2‰ in δ¹⁸O).

原理：Delta射线同位素比值红外光谱仪能够测定CO2的δ13C和δ18O值。测量是根据内部参考气体标准校准的。对于离散碳酸盐或溶解无机碳（DIC）样品，制造商建议针对两种同位素不同的碳酸盐标准材料进行校准（即两点校准）。在这里，我们表明这种方法是不够的，因为测量值可能在测量运行的持续时间内显著漂移（即，在大约24小时内58个样本）。方法：我们开发了一种新的测量程序，采用三点校准和紧密的标准支架。此外，我们还提供了一个R代码来自动评估和校准测量数据。结果：我们的标准括号法可以有效地校正内部校准数据不能解释的1‰以上的漂移。由两套标准包夹的四个样品的三点校准提供了最高的精度和准确性，也就是说，我们的碳酸盐样品的可重复性最高。第三个标准使校准曲线稳定，能够更好地识别个别异常值。结论：我们的标准包套方法使方解石和DIC的13C和δ18O值在大范围内（δ13C约为-37‰至+2‰，δ18O约为-25‰至-2‰）准确和精确。

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引用次数: 0

High Spatial Resolution (< 10 μm) Zircon SIMS Zr Isotope Analysis 高空间分辨率（< 10 μm）锆石SIMS Zr同位素分析。

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.70020

Sheng He, Yang Li, Liguang Wu, Xianhua Li

Rationale

Zircon Zr isotopic variations hold great potential for tracing magmatic crystallization and differentiation processes, although the mechanisms of Zr isotopic fractionation remain highly debated. High spatial resolution, nearly non-destructive Zr isotopic analysis of zircon, allows for a more detailed investigation of Zr isotopic variations in structurally complex or tiny zircons.

Methods

This study systematically optimized key parameters (e.g., primary beam current, beam diameter, raster size,and signal acquisition time) and further evaluated the topography effect using dynamic transfer parameters, ultimately establishing a high spatial resolution secondary ion mass spectrometry (SIMS) method for zircon Zr isotope microanalysis.

Results

The internal precision (twice the standard error [2SE]) for δ⁹⁴Zr measurements in zircon reference materials (i.e., Mudtank, Penglai, Plešovice, Tanz) ranged from 0.07‰ to 0.16‰, with external reproducibility better than 0.15‰ (twice the standard deviation [2SD]). The Zr isotopic compositions of reference materials measured by SIMS agree remarkably well with the recommended values by double-spike solution methods. Our method consumes ~0.05 ng of mineral material in a single spot analysis with a high spatial resolution of ~10 × 9 μm² and a pit depth of ~0.5 μm.

Conclusions

This nearly nondestructive technique is suitable for analyzing structurally complex or precious samples, such as zircon from lunar soil, advancing the study of magmatic processes.

理论基础：锆石Zr同位素变化在追踪岩浆结晶和分异过程方面具有很大的潜力，尽管Zr同位素分异的机制仍然存在很大的争议。高空间分辨率、几乎无损的锆石Zr同位素分析，可以更详细地研究结构复杂或微小锆石中Zr同位素的变化。方法：系统优化主要参数（如主光束电流、光束直径、光栅尺寸、信号采集时间等），并利用动态传递参数进一步评价地形效应，最终建立高空间分辨率锆石Zr同位素微量分析的二次离子质谱（SIMS）方法。结果：Mudtank、蓬莱、Plešovice、Tanz等锆石对照品中δ94Zr测定的内部精密度（2倍标准误差[2SE]）为0.07‰~ 0.16‰，外部重现性优于0.15‰（2倍标准偏差[2SD]）。SIMS测定的标准物质的Zr同位素组成与双峰溶液法的推荐值吻合得非常好。该方法在单点分析中消耗~0.05 ng矿物材料，空间分辨率为~10 × 9 μm2，坑深为~0.5 μm。结论：这种近乎无损的方法适用于分析月球土壤中锆石等结构复杂或珍贵的样品，促进了岩浆过程的研究。

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引用次数: 0

UHPLC-MS/MS Comprehensive Phytochemical Investigation of Niphidium crassifolium Rhizome: Bioactivity Assessment With Insights Into In Vitro Antioxidant and Antibacterial Potentials 高效液相色谱-质谱联用/质谱联用综合植物化学研究：体外抗氧化和抗菌活性评价

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.70014

Marco Rolando Aronés Jara, Rosy Yesela Mancilla Santa Cruz, Kirianova Godoy Bautista, Edgar Cárdenas Landeo, Edith Eveling Conislla Cáceres, Hugo Roberto Luna Molero, Juan Clímaco Paniagua Segovia, Anas Rashid, María Segunda Aurora Prado

Rationale

Niphidium crassifolium (Linnaeus) Lellinger is a fern from the Polypodiaceae family, native to Central and South America, with traditional uses in herbal medicine. Despite its recognized ethnomedical value, its phytochemical composition has not been extensively studied. This pioneering work aimed to determine the metabolite profile from rhizomes of N. crassifolium, to quantify the contents of phenols and flavonoids, and to evaluate their antioxidant and antibacterial activities.

Methods

Metabolite characterization was performed using LC-MS/MS, while radical scavenging activity (DPPH^• and ABTS^•+ assays) was used to estimate in vitro antioxidant potential. Trolox was used as reference standard in both assays. Phenolic and flavonoid contents as well as antioxidant activity were evaluated in four anatomical parts: complete rhizome, proximal rhizome, distal rhizome, and adventitious root.

Results

This study identified the presence of saponins, phytoecdysteroids, flavones, phenolic acids, and phenolic glycosides. Proximal rhizome exhibited the highest phenolic content (264.6 ± 0.15 mg GAE/g), whereas adventitious root showed the highest flavonoid content (54.0 ± 0.47 mg RUE/g). Median effective concentration of proximal rhizome was 50.4 ± 0.03 μg/mL (DPPH^•) and 310.7 ± 1.9 μg/mL (ABTS^•+), compared to Trolox values of 37.4 ± 0.01 μg/mL and 155.0 ± 0.3 μg/mL, respectively (p < 0.05). Despite slightly higher EC₅₀ values than Trolox, proximal rhizome's antioxidant capacity was statistically significant (p < 0.05). Plant exhibited selective antibacterial activity against Gram-positive bacteria, particularly Staphylococcus aureus ATCC 6538 (inhibition halo, 16.5 ± 0.09 mm; minimum inhibitory concentration, 13 370 μg/mL) and Bacillus spizizenii ATCC 6633 (inhibition halo, 12.6 ± 0.40 mm; minimum inhibitory concentration, 3 230 μg/mL).

Conclusions

These findings underscore the value of N. crassifolium as a promising source of antioxidant and antibacterial compounds. Data support its ethnomedical applications and underscore the potential for development into natural therapeutic agents targeting oxidative stress and Gram-positive infections that pave the way for future pharmaceutical and nutraceutical development.

理论依据：蛇耳蕨是水蛭科的一种蕨类植物，原产于中美洲和南美洲，传统上用于草药。尽管其具有公认的民族医学价值，但其植物化学成分尚未得到广泛研究。本研究旨在测定石竹根状茎的代谢产物，定量测定石竹根状茎中酚类和类黄酮的含量，并评价其抗氧化和抗菌活性。方法：采用LC-MS/MS进行代谢物表征，同时采用自由基清除活性（DPPH•和ABTS•+测定）评估体外抗氧化潜力。两项检测均以Trolox为参比标准品。以全根茎、根茎近端、根茎远端和不定根4个解剖部位测定其酚类和类黄酮含量及抗氧化活性。结果：本研究确定了皂苷、植物甾体、黄酮、酚酸和酚苷的存在。近根中酚类含量最高（264.6±0.15 mg RUE/g），不定根中黄酮类含量最高（54.0±0.47 mg RUE/g）。近端根茎中位有效浓度分别为50.4±0.03 μg/mL （DPPH•）和310.7±1.9 μg/mL (ABTS•+)，而Trolox分别为37.4±0.01 μg/mL和155.0±0.3 μg/mL (p < 0.05)，其抗氧化能力显著高于Trolox (p < 0.05) （p < 0.05）。数据支持其民族医学应用，并强调了开发针对氧化应激和革兰氏阳性感染的天然治疗剂的潜力，为未来的制药和营养保健开发铺平了道路。

{"title":"UHPLC-MS/MS Comprehensive Phytochemical Investigation of Niphidium crassifolium Rhizome: Bioactivity Assessment With Insights Into In Vitro Antioxidant and Antibacterial Potentials","authors":"Marco Rolando Aronés Jara, Rosy Yesela Mancilla Santa Cruz, Kirianova Godoy Bautista, Edgar Cárdenas Landeo, Edith Eveling Conislla Cáceres, Hugo Roberto Luna Molero, Juan Clímaco Paniagua Segovia, Anas Rashid, María Segunda Aurora Prado","doi":"10.1002/rcm.70014","DOIUrl":"10.1002/rcm.70014","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p><i>Niphidium crassifolium</i> (Linnaeus) Lellinger is a fern from the <i>Polypodiaceae</i> family, native to Central and South America, with traditional uses in herbal medicine. Despite its recognized ethnomedical value, its phytochemical composition has not been extensively studied. This pioneering work aimed to determine the metabolite profile from rhizomes of <i>N. crassifolium</i>, to quantify the contents of phenols and flavonoids, and to evaluate their antioxidant and antibacterial activities.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Metabolite characterization was performed using LC-MS/MS, while radical scavenging activity (DPPH<sup>•</sup> and ABTS<sup>•+</sup> assays) was used to estimate in vitro antioxidant potential. Trolox was used as reference standard in both assays. Phenolic and flavonoid contents as well as antioxidant activity were evaluated in four anatomical parts: complete rhizome, proximal rhizome, distal rhizome, and adventitious root.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>This study identified the presence of saponins, phytoecdysteroids, flavones, phenolic acids, and phenolic glycosides. Proximal rhizome exhibited the highest phenolic content (264.6 ± 0.15 mg GAE/g), whereas adventitious root showed the highest flavonoid content (54.0 ± 0.47 mg RUE/g). Median effective concentration of proximal rhizome was 50.4 ± 0.03 μg/mL (DPPH<sup>•</sup>) and 310.7 ± 1.9 μg/mL (ABTS<sup>•+</sup>), compared to Trolox values of 37.4 ± 0.01 μg/mL and 155.0 ± 0.3 μg/mL, respectively (<i>p</i> < 0.05). Despite slightly higher EC<sub>50</sub> values than Trolox, proximal rhizome's antioxidant capacity was statistically significant (<i>p</i> < 0.05). Plant exhibited selective antibacterial activity against Gram-positive bacteria, particularly <i>Staphylococcus aureus</i> ATCC 6538 (inhibition halo, 16.5 ± 0.09 mm; minimum inhibitory concentration, 13 370 μg/mL) and <i>Bacillus spizizenii</i> ATCC 6633 (inhibition halo, 12.6 ± 0.40 mm; minimum inhibitory concentration, 3 230 μg/mL).</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>These findings underscore the value of <i>N. crassifolium</i> as a promising source of antioxidant and antibacterial compounds. Data support its ethnomedical applications and underscore the potential for development into natural therapeutic agents targeting oxidative stress and Gram-positive infections that pave the way for future pharmaceutical and nutraceutical development.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 6","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145809266","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

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