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Unprecedented intact radical anions, closed shell anions, cluster ions, and traditional cations and radical cations by LIFDI-MS. 用LIFDI-MS检测前所未有的完整自由基阴离子、闭壳阴离子、簇离子以及传统阳离子和自由基阳离子。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2023-02-01 DOI: 10.1177/14690667221146079
Mathias H Linden, H Bernhard Linden

Liquid injection field desorption ionization (LIFDI) proves the extraordinary softness of the ionization process combined with a convenient sample supply under the exclusion of moisture and air. LIFDI-mass spectrometry (MS) is used for organometallic and other seriously air-sensitive compounds forming intact ions without substantial fragmentation. Unprecedented molecular radical anions M-• are presented along with well-known intact M+• radical cations. Furthermore closed shell cations [C]+ and adduct ions like [M + H]+ or [M + Alkali]+ are gently transferred from the solid emitter surface into the gas phase. Anions [A]- or [M - H]- are accessible by LIFDI-MS at medium field strengths. Ion pairs [C]+[A]- are separately detected by positive and negative mode LIFDI-MS, respectively. Here we give an overview of the different ion types accessible by LIFDI-MS. For the first time the field ionization/desorption of solar cell electron acceptor compounds is shown to deliver M- and M2- radical ions.

液体注入场解吸电离(LIFDI)证明了电离过程的非凡柔软性,并在排除水分和空气的情况下方便地提供样品。lifdi -质谱(MS)用于有机金属和其他严重空气敏感的化合物,形成完整的离子,没有实质性的碎裂。前所未有的分子自由基阴离子M-•与众所周知的完整的M+•自由基阳离子一起出现。此外,闭合壳离子[C]+和加合离子[M + H]+或[M +碱]+从固体发射极表面缓慢地转移到气相。阴离子[A]-或[M - H]-在中等场强下可被LIFDI-MS检测到。离子对[C]+[A]-分别用正、负模式LIFDI-MS检测。在这里,我们概述了LIFDI-MS可访问的不同离子类型。首次证明了太阳能电池电子受体化合物的场电离/解吸可以传递M-•和M2-•自由基离子。
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引用次数: 2
Editorial. 社论。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2023-02-01 DOI: 10.1177/14690667221148578
Jürgen Grotemeyer
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引用次数: 0
Identification and characterization of selected silyl substituted silyl anions by liquid injection field desorption ionization mass spectrometry. 液体注入场解吸电离质谱法鉴定和表征硅基取代的硅基阴离子。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2023-02-01 DOI: 10.1177/14690667221139720
Thomas Lainer, Roland C Fischer, Michael Haas

Silyl anions are crucial building blocks in silicon chemistry and are frequently used in organosilicon chemistry. These so-called silanides are negatively charged three-coordinate species, isoelectronic to carbanions. In this contribution, we synthesized already literature known and unknown anionic silicon species. Here we focused on silyl substituted silyl anions with different substituted silicon atoms like hydrogen, methyl, and methoxy groups. Furthermore, we investigated these species with liquid injection field desorption ionization mass spectrometry.

硅阴离子是硅化学的重要组成部分,在有机硅化学中被广泛使用。这些所谓的硅烷是带负电的三坐标物质,与碳离子等电子。在这篇文章中,我们合成了已知和未知的阴离子硅。在这里,我们关注的是硅基取代硅基阴离子与不同取代的硅原子,如氢、甲基和甲氧基。此外,我们用液体注射场解吸电离质谱法对这些物质进行了研究。
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引用次数: 0
Positive + negative is not equal to zero: Use of negative ionisation as analyte identity confirmation tool in LC-ESI-MS analysis. 正+负不等于零:在LC-ESI-MS分析中使用负电离作为分析物身份确认工具。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-10-01 Epub Date: 2022-10-06 DOI: 10.1177/14690667221130160
Ernesto Zapata, Ivo Leito, Koit Herodes

In this study the use of negative electrospray ionisation mode as a confirmation tool for identifying derivatized amino acids using LC-ESI-MS, was evaluated. The derivatization reagent was based on azobenzene N-hydroxysuccinimide carbamate. The results indicate that even though negative ionisation mode produced less intense peaks, the ratio of peak area of quantifier ion (obtained in positive mode) to the qualifier (or identifier) ion measured in negative mode meets the requirements established by two prominent validation guidelines: SANTE/11312/2021 and 2002/657/EC. Therefore, the use of product ions obtained via negative transitions as qualifier ions, while using product ions from positive transitions as quantifier ions is a fruitful approach that widens the choice of transitions to choose from for obtaining suitable qualifier ions. This methodology was applied to the LC-ESI-MS/MS determination of amino acids in different beverages (tomato juice, watermelon juice, kvass).

在这项研究中,使用负电喷雾电离模式作为鉴定衍生氨基酸的LC-ESI-MS确认工具,进行了评估。衍生化试剂以偶氮苯n -羟基琥珀酰亚胺氨基甲酸酯为基础。结果表明,尽管负电离模式产生的峰强度较小,但定量离子(在正模式下获得)与负模式下测量的限定(或标识)离子的峰面积之比符合两个重要验证指南:SANTE/11312/2021和2002/657/EC建立的要求。因此,使用通过负跃迁获得的生成物离子作为限定离子,而使用通过正跃迁获得的生成物离子作为定量离子是一种富有成效的方法,可以拓宽跃迁的选择范围,以获得合适的限定离子。该方法适用于不同饮料(番茄汁、西瓜汁、克瓦斯)中氨基酸的LC-ESI-MS/MS测定。
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引用次数: 1
Gas Chromatography - Ion Mobility Spectrometry as a tool for quick detection of hazardous volatile organic compounds in indoor and ambient air: A university campus case study. 气相色谱-离子迁移谱法作为快速检测室内和环境空气中有害挥发性有机化合物的工具:一个大学校园案例研究。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-10-01 Epub Date: 2022-10-05 DOI: 10.1177/14690667221130170
Pedro Catalão Moura, Valentina Vassilenko

Society's concerns about the citizens' exposure to possibly dangerous environments have recently risen; nevertheless, the assessment of indoor air quality still represents a major contemporary challenge. The volatile organic compounds (VOCs) are among the main factors responsible for deteriorating air quality conditions. These analytes are very common in daily-use environments and they can be extremely hazardous to human health, even at trace concentrations levels. For these reasons, their quick detection, identification, and quantification are crucial tasks, especially for indoor and heavily-populated scenarios, where the exposure time is usually quite long. In this work, a Gas Chromatography - Ion Mobility Spectrometry (GC-IMS) device was used for continuous monitoring indoor and ambient air environments at a large-scale, due to its outstanding levels of sensibility, selectivity, analytical flexibility, and almost real-time monitoring capability. A total of 496 spectra were collected from 15 locations of a university campus and posteriorly analysed. Overall, 23 compounds were identified among the 31 detected. Some of them, like Ethanol and 2-Propanol, were reported as being very hazardous to the human organism, especially in indoor environments. The achieved results confirmed the suitability of GC-IMS technology for air quality assessment and monitoring of VOCs and, more importantly, proved how dangerous indoor environments can be in scenarios of continuous exposure.

最近,社会对公民可能暴露在危险环境中的担忧有所上升;然而,室内空气质量的评估仍然是当代的一个重大挑战。挥发性有机化合物(VOCs)是造成空气质量恶化的主要因素之一。这些分析物在日常使用环境中非常常见,即使浓度极低,也可能对人体健康造成极大危害。由于这些原因,它们的快速检测、识别和量化是至关重要的任务,特别是在室内和人口稠密的情况下,暴露时间通常相当长。在这项工作中,气相色谱-离子迁移谱法(GC-IMS)设备被用于大规模的室内和环境空气环境的连续监测,因为它具有出色的灵敏度、选择性、分析灵活性和几乎实时的监测能力。从某大学校园的15个地点共收集了496个光谱并进行了后期分析。总的来说,在31个检测到的化合物中鉴定出23个化合物。其中一些,如乙醇和2-丙醇,据报道对人体有机体非常危险,特别是在室内环境中。取得的结果证实了GC-IMS技术在空气质量评估和VOCs监测中的适用性,更重要的是,证明了室内环境在持续暴露的情况下是多么危险。
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引用次数: 10
Quantitative evaluation and pharmacokinetic characteristics of the irreversible BTK inhibitor zanubrutinib in mouse plasma using LC-MS/MS. 用LC-MS/MS定量评价不可逆BTK抑制剂扎鲁替尼在小鼠血浆中的药动学特征。
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-06-01 Epub Date: 2022-09-22 DOI: 10.1177/14690667221128934
Kai Cheng, Junsong Wei, Jianrong Kou, Huining You, Min Li, Weiyi Feng

Zanubrutinib (BGB-3111) belongs to the class of irreversible inhibitors of Bruton's tyrosine kinase (BTK) for treating B-cell malignancies. A validated assay with excellent sensitivity, selectivity, and simplicity is required to measure plasma concentration and investigate its pharmacokinetics. The plasma of mice containing zanubrutinib and roxithromycin (internal standard) was processed with acetonitrile for protein precipitation. Then the supernatant was analyzed by high-performance liquid chromatography coupled with a triple quadrupole mass spectrometer using electrospray ionization in the positive mode. Zanubrutinib was given to mice intragastrically at 30 mg/kg to determine its pharmacokinetic parameters. The method was verified and showed good linearity in the range of 0.1-100 ng/mL. The method's sensitivity, accuracy, and precision were all within acceptable bounds. By this method, the pharmacokinetic profile of zanubrutinib in mouse plasma was measured.

Zanubrutinib (BGB-3111)属于布鲁顿酪氨酸激酶(BTK)的不可逆抑制剂,用于治疗b细胞恶性肿瘤。需要一种具有极好的灵敏度、选择性和简单性的有效测定方法来测量血浆浓度并研究其药代动力学。用乙腈对含有扎鲁替尼和罗红霉素(内标)的小鼠血浆进行蛋白质沉淀处理。上清液采用高效液相色谱联用三重四极杆质谱仪进行正模式电喷雾电离分析。以30 mg/kg剂量给药扎鲁替尼,测定其药代动力学参数。方法在0.1 ~ 100 ng/mL范围内呈良好的线性关系。方法的灵敏度、准确度、精密度均在可接受范围内。用该方法测定了扎鲁替尼在小鼠血浆中的药动学特征。
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引用次数: 1
Liquid biopsy markers for early diagnosis of brain metastasis patients with breast cancer by metabolomics 代谢组学在乳腺癌脑转移患者早期诊断中的应用
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-04-01 DOI: 10.1177/14690667221093871
Özge Özer, E. Nemutlu, Tuba Reçber, C. C. Eylem, B. Aktaş, S. Kır, A. Kars, S. Aksoy
Introduction: Breast cancer is the most common cancer in women and is the second most common cause of cancer related mortality. Metabolomics, the identification of small metabolites, is a technique for determining the amount of these metabolites. Objectives: This study aimed to identify markers for the early diagnosis of brain metastasis by metabolomic methods in breast cancer patients. Methods: A total of 88 breast cancer patients with distant metastases were included in the study. The patients were divided into two groups according to their metastasis status: patients with brain metastases and distant metastases without any brain metastases. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-qTOF-MS) and gas chromatography-mass spectrometry (GC-MS) analysis methods were used for metabolomic analyses. Results: 33 of them, 88 patients had brain metastasis, and 55 patients had distant metastases without brain metastasis. A total of 72 and 35 metabolites were identified by the GC-MS and LC-qTOF-MS analysis, respectively. 47 of them were found to be significantly different in patients with brain metastasis. The pathway analysis, performed with significantly altered metabolites, showed that aminoacyl tRNA biosynthesis, valine, leucine and isoleucine biosynthesis, alanine, aspartate, and glutamate metabolism, arginine biosynthesis, glycine, serine, and threonine metabolism pathways significantly altered in patients with brain metastasis. Predictive accuracies for have identifying the brain metastasis were performed with receiver operating characteristic (ROC) analysis, and the model with fifteen metabolites has 96.9% accuracy. Conclusions: While these results should be supported by prospective studies, these data are promising for early detection of brain metastasis with markers in liquid biopsy samples.
简介:乳腺癌是女性中最常见的癌症,也是导致癌症相关死亡的第二大常见原因。代谢组学是鉴定小代谢物的一种技术,用于确定这些代谢物的数量。目的:本研究旨在通过代谢组学方法确定乳腺癌患者脑转移的早期诊断标志物。方法:对88例乳腺癌远处转移患者进行研究。根据转移情况将患者分为两组:脑转移患者和未发生脑转移的远处转移患者。代谢组学分析采用液相色谱-四极杆飞行时间质谱(LC-qTOF-MS)和气相色谱-质谱(GC-MS)分析方法。结果:其中33例发生脑转移88例,远处转移55例无脑转移。GC-MS和LC-qTOF-MS分别鉴定出72种和35种代谢物。其中47例在脑转移患者中存在显著差异。代谢产物发生显著改变的通路分析显示,脑转移患者的氨酰基tRNA生物合成、缬氨酸、亮氨酸和异亮氨酸生物合成、丙氨酸、天冬氨酸和谷氨酸代谢、精氨酸生物合成、甘氨酸、丝氨酸和苏氨酸代谢途径发生显著改变。采用受试者工作特征(ROC)分析对脑转移的预测准确性进行了验证,其中包含15种代谢物的模型准确率为96.9%。结论:虽然这些结果应该得到前瞻性研究的支持,但这些数据对于用液体活检样本中的标志物早期检测脑转移是有希望的。
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引用次数: 0
Sample preparation and quantification of polar drug, allopurinol, in human plasma using LCMSMS 用LCMSMS测定人血浆中极性药物别嘌呤醇的制备和定量
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-04-01 DOI: 10.1177/14690667221105837
Emily Yii Ling Wong, Gabriel Onn Kit Loh, Chen Zhu Goh, Y. Tan, Sharon Shi Min Ng, Kian Boon Law, Kit Yee Cheah, Hani Farhana Mohd, K. Peh
A fast, selective and reproducible LC-MS/MS method with simple sample preparation was developed and validated for a polar compound, allopurinol in human plasma, using acyclovir as internal standard (IS). Chromatographic separation was achieved using Agilent Poroshell 120 EC-C18 (100 × 2.1 mmID, 2.7 µm) analytical column. The mobile phase was comprised of 0.1%v/v formic acid-methanol (95:05; v/v), at a flow rate of 0.45 mL/min. The effect of different protein precipitation agents used in sample preparation such as methanol, acetonitrile, a mixture of acetonitrile-methanol and a mixture of acetonitrile-acetone were evaluated to optimize the extraction efficiency of allopurinol and IS. The use of acetone-acetonitrile (50:50, v/v) as protein precipitating agent shortened the sample preparation time and improved the recovery of allopurinol to above 93%. The IS-normalised matrix factors at two concentration levels were 1.0, with CV of 5.1% and 4.2%. Allopurinol in plasma was stable at benchtop for 24 h, in autosampler tray for 48 h, in instrumentation room for 48 h, in freezer after 7 freeze-thaw cycles and in freezer for 140 days. Allopurinol stock standard solutions were stable for 140 days at room temperature and in the chiller. The short sample run time of the validated bioanalytical method allowed high throughput analysis of plasma samples in pharmacokinetic study of an allopurinol formulation. The robustness and reproducibility of the bioanalytical method was reaffirmed through incurred sample reanalysis (ISR).
以阿昔洛韦为内标,建立了一种快速、选择性、重复性好、样品制备简单的液相色谱-质谱联用(LC-MS/MS)方法,并对其进行了验证。色谱分离采用Agilent Poroshell 120 EC-C18 (100 × 2.1 mmID, 2.7µm)分析柱。流动相为0.1%v/v甲酸-甲醇(95:05;v/v),流速为0.45 mL/min。考察了甲醇、乙腈、乙腈-甲醇混合物和乙腈-丙酮混合物等不同蛋白质沉淀剂对样品制备的影响,以优化别嘌呤醇和IS的提取效率。采用丙酮-乙腈(50:50,v/v)作为蛋白质沉淀剂,缩短了样品制备时间,别嘌呤醇的回收率提高到93%以上。两种浓度水平下is归一化基质因子为1.0,CV分别为5.1%和4.2%。血浆中的别嘌呤醇在实验台上稳定24 h,在自动进样器托盘中稳定48 h,在仪器室中稳定48 h,冻融循环7次后冷冻,冷冻140天。别嘌呤醇原液标准液在室温和冷水机中稳定140天。验证的生物分析方法的样品运行时间短,允许在别嘌呤醇制剂的药代动力学研究中对血浆样品进行高通量分析。通过发生的样品再分析(ISR)验证了生物分析方法的稳健性和重复性。
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引用次数: 1
Determination of arsenic, cadmium, mercury, lead and nickel as elemental impurities in atorvastatin calcium by inductively coupled mass spectrometer 电感耦合质谱法测定阿托伐他汀钙中砷、镉、汞、铅和镍等元素杂质
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-04-01 DOI: 10.1177/14690667221105835
A. Pal, R. Sundararajan
Atorvastatin calcium is employed as front-line treatment for cardiovascular diseases. According to the international conference on harmonization (ICH) guideline ICH Q3D, elemental impurities can come into drug products from various sources. These elemental impurities do not have any therapeutic benefit to the end-user. On the contrary, it harms the normal physiological system. Class 1 elements like arsenic, cadmium, mercury, and lead are inorganic impurities that can cause toxic effects on the human body. Nickel was used as a catalyst during the synthesis process of atorvastatin calcium. It comes under the Class-2A, can cause toxicity to humans, and must be quantified. A simple, fast, reliable inductively coupled plasma mass spectrometric method for the estimation of elemental impurities like arsenic, cadmium, mercury, lead, and nickel in atorvastatin calcium by open sample digestion technique was developed and validated in accordance with ICH Q3D and USP < 232 > and USP <233 > general chapter. Internal standards like indium, terbium, thallium, bismuth and yttrium were used to correct the non-spectral interferences that were generated during analysis. Gold was added to all solutions as it preserves mercury by amalgamation. The system performance was evaluated every time my performing system suitability parameters. The limits for all the elements were fixed in accordance with ICH Q3D. The limit of detection and the limit of quantification for all the five elements were estimated. Method specificity was proven by checking for interferences due to the sample matrix and other elements. Linearity of each element in standards was established from 25% to 200% of sample concentration, and correlation coefficients were found to be not less than 0.999. The accuracy of the method was demonstrated at three spiking levels at 50%, 100%, and 150% of the J-value for all the elements. The recoveries for all elements at each level were within the range of 90–120%. Method precision was proved at 100% J-value. The relative standard deviation of all elements was less than 5%. It concludes that this newly developed and validated reliable inductively coupled plasma mass spectrometric method for estimating of elemental impurities like arsenic, cadmium, mercury, lead, and nickel in atorvastatin calcium was within the permitted limit and suitable for routine use.
阿托伐他汀钙被用作心血管疾病的一线治疗。根据国际协调会议(ICH)指南ICH Q3D,元素杂质可以从各种来源进入药品。这些元素杂质对最终用户没有任何治疗益处。相反,它损害了正常的生理系统。第一类元素,如砷、镉、汞和铅,是对人体有毒的无机杂质。以镍为催化剂合成了阿托伐他汀钙。它属于2a类,对人类有毒性,必须量化。建立了一种简单、快速、可靠的电感耦合等离子体质谱法,利用开放样品消解技术测定阿托伐他汀钙中砷、镉、汞、铅、镍等元素杂质,并按照ICH Q3D、USP和USP通章进行了验证。内部标准物如铟、铽、铊、铋和钇被用来校正分析过程中产生的非光谱干扰。所有的溶液中都加入了金,因为它可以通过汞的混合保存汞。每次执行系统适用性参数时,都会对系统性能进行评估。所有元素的限量根据ICH Q3D确定。对五种元素的检出限和定量限进行了估计。通过检查样品基质和其他元素的干扰,证明了方法的特异性。在样品浓度为25% ~ 200%的范围内建立了各元素的线性关系,相关系数不小于0.999。在所有元素的j值的50%、100%和150%三个峰值水平上证明了该方法的准确性。加样回收率在90 ~ 120%范围内。方法精密度在100% j值。各元素的相对标准偏差均小于5%。结果表明,新建立的电感耦合等离子体质谱法测定阿托伐他汀钙中砷、镉、汞、铅、镍等元素杂质在允许范围内,适合常规使用。
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引用次数: 0
Fragmentation analysis of O-specific polysaccharide from bacteria Vibrio cholerae O139 by MALDI-TOF and LC/ESI-MS/MS O139霍乱弧菌O-特异性多糖的MALDI-TOF和LC/ESI-MS/MS片段分析
IF 1.3 4区 化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Pub Date : 2022-04-01 DOI: 10.1177/14690667221099119
Filip Pančík, Z. Pakanová, Jana Mečárová, Alžbeta Čížová, S. Bystrický, S. Kozmon, P. Baráth
Cholera is a life-threatening diarrhoeal disease caused by ingestion of Vibrio cholerae . There are at least 200 serogroups of V. cholerae but only two of them are causing epidemics – O1 and O139 serogroups. Fragmentation analysis of O-antigen, also known as O-specific polysaccharide (OSP), from lipopolysaccharide (LPS) is important to obtain new information about its structure, such as fragmentation patterns and fragment structures. In the present study, OSP and core (OSPc) structure from V. cholerae O139 was studied using matrix-assisted laser desorption ionization (MALDI)-time of flight (TOF) and direct injection electrospray ionization (ESI)-MS methods. MALDI-TOF analysis was performed in positive-ion reflectron mode, while ESI-MS was performed in negative ionization mode. ESI-MS analysis was followed by ESI-MS/MS analysis. Using this analytical approach, we managed to obtain two possible fragmentation pathways of OSP from V. cholerae O139 . Mutual sign of these two pathways is shortening the length of the oligosaccharide by neutral loss of monosaccharide residues. Additionally, liquid chromatography-MS analysis was performed to separate depicted molecular forms of OSPc.
霍乱是一种由摄入霍乱弧菌引起的危及生命的腹泻病。霍乱弧菌至少有200个血清群,但其中只有两个引起流行病——O1和O139血清群。对脂多糖(LPS)中的O-抗原(也称为O-特异性多糖(OSP))进行片段化分析,对于获得有关其结构的新信息,如片段化模式和片段结构,具有重要意义。本研究采用基质辅助激光解吸电离(MALDI)-飞行时间(TOF)和直接注射电喷雾电离(ESI)-MS方法对O139霍乱弧菌的OSP和核心(OSPc)结构进行了研究。MALDI-TOF分析在正离子反射镜模式下进行,而ESI-MS分析在负电离模式下进行。ESI-MS分析之后是ESI-MS/MS分析。使用这种分析方法,我们成功地从O139霍乱弧菌中获得了OSP的两种可能的裂解途径。这两种途径的相互标志是通过单糖残基的中性损失缩短低聚糖的长度。此外,进行液相色谱-质谱分析以分离所描述的OSPc的分子形式。
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引用次数: 0
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European Journal of Mass Spectrometry
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