【干货】DART 技术速递 - 2016春季回归！

WHAT'S NEW WITH DART® MS?                   

The Latest Developments in DART MS

Included in this newsletter:

本则速递中包含有：

(Un)targeted Scanning of Locks of Hair for Drugs of Abuse by Direct Analysis in Real Time-High-Resolution Mass Spectrometry

实时直接分析高分辨质谱技术扫描监测毛发里的滥用药物

Analysis of carbohydrates in Fusarium verticillioides using size-exclusion HPLC-DRI and DART-TOF-MS

空间体积排阻 HPLC-DRI 和 DART-TOF-MS 联用分析镰刀菌中的碳水化合物

Petroleomics by Direct Analysis in Real Time-Mass Spectrometry

实时直接分析质谱技术研究石油组学

Recent DART Publications

最近发表的 DART 文章

(Un)targeted Scanning ofLocks of Hair for Drugs of Abuse by Direct Analysis in Real Time-High-Resolution Mass Spectrometry

实时直接分析高分辨质谱技术扫描监测毛发里的滥用药物

Wilco F. Duvivier, Marc R. van Putten, Teris A. van Beek, and Michel W.F. Nielen

Forensic hair evidence can be used to obtain retrospective timelines of drug use by analysis of hair segments. However, this is a laborious and time-consuming process, and mass spectrometric(MS) imaging techniques,which show great potential for single-hair targeted analysis, are less useful due to differences in hair growth rate between individual hairs. As an alternative, a fast untargeted analysis method was developed that uses direct analysis in real time-high-resolution mass spectrometry (DART-HRMS) to longitudinally scan intact locks of hair without extensive sample preparation or segmentation. The hair scan method was validated for cocaine against an accredited liquid chromatography/tandem mass spectrometry (LC/MS/MS) method. The detection limit for cocaine in hair was found to comply with the cut off value of 0.5 ng/mg recommended by the Society of Hair Testing; that is, the DART hair scan method is amenable to forensic cases. Under DART conditions, no significant thermal degradation of cocaine occurred.The standard DART spot size of 5.1 ±1.1 mm could be improved to 3.3 ± 1.0 mm, corresponding to approximately 10 days of hair growth, by using a high spatial resolution exit cone. By use of data-dependent product ion scans, multiple drugs of abuse could be detected in a single drug user hair scan with confirmation of identity by both exact mass and MS/HRMS fragmentation patterns. Furthermore, full-scan high-resolution data were retrospectively interrogatedversus a list of more than 100 compounds and revealed additional hits and temporal profiles in good correlation with reported drug use.

通过分析毛发片段的法医证据可以追溯药物使用的时限。然而，这是一个费力和耗时的过程，并且由于每根毛发生长速率的差异，使针对单根毛发目标性分析有巨大潜力的质谱成像技术不太有用。作为一种替代，一种快速非目标性的分析方法发展起来，使用实时直接分析高分辨质谱（DART-HRMS）纵向扫描完好的固定毛发，无需大量的样品制备或分段。这种毛发扫描方法已经针对可卡因用液相色谱串联质谱的方法进行验证。头发中可卡因的检出限遵守毛发测试学会推荐的0.5ng/mg 的临界值，也就是说，DART毛发扫描方法适合于法医案例。在DART条件下，可卡因无显著热降解的发生。标准的 DART 样斑的大小5.1±1.1mm 可以提高到3.3±1.0mm 通过使用高空间分辨出口椎体,相当于生长约10天的毛发。使用数据依赖性产物离子扫描，多种药物的滥用可以在一个吸毒者的头发扫描中被检测出来，利用准确质量数和 MS/HRMS 碎片。此外，全扫描高分辨率的数据可以回溯超过100个化合物的列表，显示出额外的命中和时间分布在已报到的药物使用中呈现良好的相关性。

Analysis of carbohydrates in Fusarium verticillioides using size-exclusion HPLC-DRI and DART-TOF-MS

空间体积排阻 HPLC-DRI 和 DART-TOF-MS 联用分析镰刀菌中的碳水化合物

Ethan Roberts,   Beth Boudreau,   Daren Brown, Kristi McQuade and   Edward Remsen

Direct analysis in real time ionization-time-of-flight-mass spectrometry (DART-MS) and size-exclusion HPLC - DRI are used,respectively, to qualitatively and quantitatively determine the carbohydrates extracted from the corn rot fungus Fusarium verticillioides. In situ permethylation in the DART beam forms tri-methylammonium adducts of the carbohydrates, which enables positive ion MS detection and analysis of these compounds in either whole fungal extracts or size-exclusion separated HPLC fractions of the extracts.This method detects the disaccharide trehalose at concentrations greater than3.0 ppm. Additionally, this procedure allows for analysis of glucose as well as the sugar alcohols mannitol, arabitol, and glycerol. There liability of the DART-MS method is confirmed by the absence of trehalose in amutant strain of F. verticillioides lacking the gene for trehalose-6-phosphate synthase.The capabilities demonstrated here suggest that the DART-MS method, inconjunction with size-exclusion HPLC, is an effective approach for the analysis of saccharide biomarkers in fungi.

利用实时直接分析电离-飞行时间质谱（DART-MS）和空间体积排阻 HPLC– DRI 技术，定性和定量地检测从玉米腐菌镰刀菌中提取的碳水化合物。原位完全甲基化在 DART 气流束中形成三甲基铵加合物的碳水化合物，可用正离子质谱检测分析整个真菌提取物中的化合物，或者空间体积排阻HPLC分级分离提取物。该方法可检测浓度大于3.0ppm的双糖海藻糖。此外，这个过程可分析葡萄糖以及糖醇甘露醇，阿糖醇和甘油。DART-MS 方法的可靠性是由 F.verticillioides 的突变菌株缺乏海藻糖证实的，这种菌株缺乏海藻糖-6-磷酸合成酶的基因。这个功能展示意味着 DART-MS 与空间体积排阻 HPLC 相结合是分析真菌中糖类生物标记物的有效方法。

Petroleomics by Direct Analysis in Real Time-Mass Spectrometry

实时直接分析质谱技术研究石油组学

Romão, Tose, Vaz, Sama, Lobinski, Giusti, Carrier and Bouyssiere

The analysis of crude oil and its fractions by applying ambient ionization techniques remain sunder explored in mass spectrometry (MS). Direct analysis in real time (DART) in the positive-ion mode was coupled to alinear quadrupole ion trap Orbitrap mass spectrometer (LTQ Orbitrap) to analyze crude oil, paraffin samples, and porphyrin standard compounds. The ionization parameters of DART-MS were optimized for crude oil analysis. DART-MS rendered the optimum conditions ofthe operation using paper as the substrate, T = 400°C, helium as the carriergas, and a sample concentration ≥6 mg mL-1. In the crude oils analysis, the DART(+)-Orbitrap mass spectra detected the typical N, NO, and O-containing compounds. In the paraffin samples, oxidized hydrocarbon species(Oxclasses, where x = 1-4) with double-bond equivalent of 1-4 were detected, and their structures and connectivity were confirmed by collision-induced dissociation (CID) experiments. DART(+)-MS has identified the porphyrin standard compounds as [M + H]+ ions of m/z 615.2502 and 680.1763, where M = C44H30N4 and C44H28N4OV, respectively, based on the formula assignment and by phenyl losses observed on CID experiments.

应用原位电离质谱技术分析原油及其分级产物仍然是一个未开发的领域。正离子模式 DART 偶联一个线性四极杆离子阱轨道阱联用质谱仪（LTQOrbitrap）分析原油，石蜡样品和卟啉的标准化合物。DART-MS 的电离参数为原油分析进行了优化。DART-MS 呈现的操作最佳条件是以纸作为基板，T=400℃，以氦作为载气，样品浓度≥6 mg/mL。在原油的分析中，DART(+)-Orbitrap质谱图可检测典型的 N，NO，和含氧化合物。在石蜡样品中，双键当量1-4的氧化的烃类物质（Ox类，其中x=1-4）被检测出来，它们的结构和成键通过碰撞诱导解离（CID）实验来证实。DART(+)-MS 已经鉴定卟啉标准化合物[M+H] + 的离子m/z 分别为615.2502 和680.1763，其中 M= C44H30N4 and C44H28N4OV,此公式分配来自于 CID 实验中观察到的苯基损失。

About ASPEC

关于华质泰科

ASPEC develops solutions to help advance innovations in real-time science and technology. We support scientists in chemical and life science industries by offering premier bio-analytical instruments, consulting and services. We are conducting sales, marketing, and support functions as an exclusive distributor of IonSense, Advion, CovalX, Phytronix, and many others in the Greater China region. ASPEC founded and co-organized the Ambient Ionization Mass Spectrometry Conference China, since 2013.

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