Entwicklung einer Multi-Purpose Ionenquelle für die AP-MS sowie Design und Anwendung von APLI-Ionisationslabeln
Entwicklung einer Multi-Purpose Ionenquelle für die AP-MS sowie Design und Anwendung von APLI-Ionisationslabeln
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AP-MS 的多用途离子发生器设计和 APLI 电离标签的研究
DOI：
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发表时间：
2009
期刊：
影响因子：
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通讯作者：
Ralf Schiewek
中科院分区：
文献类型：
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作者：
Ralf Schiewek
大气压激光电离(APLI)是由伍珀塔尔大学开发的
作为一种灵敏的常压电离法分析非极性芳烃
碳氢化合物。液相色谱(LC)与APLI的联用首先是通过
一种LC-APLi-(TOF)MS形式的Q-TOF Ultima(Waters)仪器，因为它的伟大
分离动力，气相色谱提供了一种有趣的替代LC的方法。一个计划是
因此起草了将气相色谱仪与大气压离子源相耦合的草案。
APLI的Q-TOF Ultima。为此，适当的电加热传送线
是建造的。这条传送线的前端可以安装，而不是
在未改装的大气压离子源上的挥发阶段。这个
运行信号源所需的参数，如信号源内的气体量和
质谱仪上的设置进行了优化。这种新型联轴器的效率是
通过对一些标准(多环芳烃和杂多环芳烃)的分析证明了这一点。
在这种成功耦合的基础上，APLI还与另一个大气压耦合
质谱仪(MicrorOTOF，Bruker Daltonics)。为此，一种新的离子源是
为质谱计开发的，取代了标准的质谱仪。其核心组件是
新的源代码，可用于LC和GC版本的APLI-(TOF)MS，是一个
立方体状的源体，具有多个孔。各种附加组件，如
或新开发的传送线的挥发阶段，可以是
安装在身体上。在对重要参数进行优化后，一些
标准样品和实际样品均用LC-APLI-(TOF)MS和GCAPLI-(
TOF)MS系统，以显示这种耦合的潜力。因此，除了
几种用于制造有机发光二极管的芳香族齐聚物，其
很难用其他方法分析，过渡金属络合物用作三重态发射体
成功地用LC-APLI-(TOF)MS进行了分析
对GC-APLI-(TOF)MS、几种多环芳烃和杂多环芳烃标准品进行了分析，并对结果进行了分析。
尿液中检测到代谢物1-羟基芘。对于大黄素，检出限为0.5ng/L
进样量为2µL。
为了利用这种灵活耦合的优点，其中昂贵的高分辨率
质谱仪作为检测器同时用于各种色谱应用
通过三种重要的大气压电离方法(ESI、APCI、APPI)，这些
方法被融入到设计中。此外，GC-Transfer的改进版本
LINE被开发出来。这是一种多用途API源(MPIS)的新设计
由Bruker Daltonics公司商用，作为一种灵活的离子源
大气压质谱仪。
在各种电离方法之间切换很方便，只需要
可在源体的孔口处交换可选部件。例如，要
从GC-APLI-(TOF)MS切换到GC-APCI-(TOF)MS，仅替换了一个石英窗
通过APCI针组件。LC和GC之间的切换也可以采用相同的方式：
在这里，只有传送线必须更换为盲法兰。在这个设计中，电离
这些方法可以单独应用，也可以组合应用，作为真正的多模电离
(例如，同时使用APLI和APCI)。各个模式的效率是
用几个标准进行了论证。有了这个源，电离技术，如ESI，
APCI、APPI和APLI可用于LC和GC。对于LC，额外的多模
可以使用APLI+ESI和APLI+APCI两种电离技术。
APLI是一种选择性电离非极性芳香族化合物的方法。一方面，这一点
表示对该方法的一般适用性的限制，但另一方面，它
使得在复杂的基质中选择性地电离这类化合物成为可能。因此
开发了LC-APLI的电离标记和相应的衍生化策略。
(TOF)MS和GC-APLI-(TOF)MS这些电离标记是芳香族化合物，可以
以高灵敏度被检测。它们具有与非芳香族共价偶联的锚基
分析物。然后，可以用APLI灵敏地检测到该导数。关于……的研究
几种衍生物在大气压下的REMPI谱表明它们不存在。
与标签本身的差异很大，这表明电子
衍生物中芳香族体系的比例不受
分析物。展示了APLI电离标记在LC-APLI中的实际应用。
(TOF)MS和GC-APLI-(TOF)MS通过对Brij®72和
PEG1000和植物油中脂肪酸含量的测定及一种技术
脂肪酒精混合物。
Atmospheric-Pressure Laser Ionization (APLI) was developed at the University of Wuppertal
as a sensitive atmospheric-pressure ionisation method for the analysis of non-polar aromatic
hydrocarbons. The coupling of liquid chromatography (LC) with APLI was first realised with
a Q-TOF Ultima (Waters) instrument in the form of LC-APLI-(TOF)MS. Because of its great
separating power, gas chromatography presents an interesting alternative to LC. A plan was
therefore drafted for coupling a gas chromatograph with the atmospheric-pressure ion source
of the Q-TOF Ultima for APLI. To this end, an appropriate electrically heated transfer line
was constructed. The front end of this transfer line could be mounted instead of a
volatilisation stage on the otherwise unmodified atmospheric-pressure ion source. The
parameters necessary to operate the source, such as the amounts of gas within the source and
settings on the mass spectrometer, were optimised. The efficiency of this new coupling was
demonstrated by the analysis of a number of standards (PAHs and hetero-PAHs).
On the basis of this successful coupling, APLI was also coupled with another atmosphericpressure
mass spectrometer (micrOTOF, Bruker Daltonics). For this, a new ion source was
developed for the mass spectrometer, to replace the standard one. The central component of
the new source, which can be used for LC as well as for GC versions of APLI-(TOF)MS, is a
cube-shaped source body with several apertures. Various additional components, such as the
volatilisation stage of liquid chromatography or the newly developed transfer line, could be
mounted onto the body. After important parameters had been optimised, a number of
standards as well as real samples were analysed with both the LC-APLI-(TOF)MS and GCAPLI-(
TOF)MS systems, in order to show the potential of this coupling. Thus, in addition to
several aromatic oligomers used in the manufacture of organic light-emitting diodes, which
are difficult to analyse by other methods, transition-metal complexes used as triplet emitters
were successfully analysed by LC-APLI-(TOF)MS. Among examples of the application of
GC-APLI-(TOF)MS, several PAH and hetero-PAH standards were analysed, and the pyrene
metabolite 1-hydroxypyrene was detected in urine. For chrysene, a detection limit of 0.5 ng/L
was achieved with an injection volume of 2 µL.
In order to use the advantages of such a flexible coupling, in which the costly high-resolution
mass spectrometer serves as detector for various chromatographic applications in conjunction
with the three important atmospheric-pressure ionisation methods (ESI, APCI, APPI), these
methods were integrated into the design. In addition, an improved version of the GC-transfer
line was developed. This new design of a Multi-Purpose API-Source (MPIS) has been made
commercially available by the company Bruker Daltonics as a flexible ion source for an
atmospheric-pressure mass spectrometer.
Switching between various ionisation methods is convenient, requiring only that the
alternative components be exchanged at the apertures of the source body. For example, to
switch from GC-APLI-(TOF)MS to GC-APCI-(TOF)MS, only a quartz window is replaced
by the APCI needle assembly. Switching between LC und GC is possible in the same way:
here only the transfer line has to be replaced by a blind flange. In this design, the ionisation
methods can be applied either individually or in combination as true multimode ionisation
(e.g. APLI and APCI simultaneously). The efficiency of the individual modes was
demonstrated with several standards. With this source, ionisation techniques such as ESI,
APCI, APPI and APLI are available for both LC and GC. For LC, the additional multimode
ionisation techniques APLI+ESI and APLI+APCI can be used.
APLI is a selective method for ionising non-polar aromatic compounds. On the one hand, this
represents a limitation to the general applicability of the method, but on the other hand it
makes it possible to ionise this class of compounds selectively in a complex matrix. Therefore
ionisation labels and corresponding strategies for derivatisation were developed for LC-APLI-
(TOF)MS and GC-APLI-(TOF)MS. These ionisation labels are aromatic compounds that can
be detected with high sensitivity. They have an anchor group for covalent coupling with nonaromatic
analytes. The derivative can then be detected sensitively by APLI. A study of
REMPI spectra of several derivatives under atmospheric pressure showed that they do not
differ significantly from those of the labels themselves, which indicates that the electronic
proportion of the aromatic system of the derivative is not significantly influenced by the
analyte. The practical application of the APLI ionisation labels was showen for LC-APLI-
(TOF)MS and GC-APLI-(TOF)MS by study of a number of samples such as Brij® 72 and
PEG 1000 and by the determination of the fatty acid content of vegetable oils and a technical
fatty alcohol mixture.
影响因子：
7.4
作者：
Cech, NB;Enke, CG
通讯作者：
Enke, CG
影响因子：
7.4
作者：
Singh, G;Gutierrez, A;Blair, IA
通讯作者：
Blair, IA
研究电喷雾单四极杆质谱仪输运区的碰撞活化分解过程和光谱。
DOI：
10.1002/rcm.1290050604
发表时间：
1991
期刊：
Rapid communications in mass spectrometry : RCM
影响因子：
--
作者：
Voyksner,RD;Pack,T
通讯作者：
Pack,T