Assessing the Interplay between the Physicochemical Parameters of Ion-Pairing Reagents and the Analyte Sequence on the Electrospray Desorption Process for Oligonucleotides.
Assessing the Interplay between the Physicochemical Parameters of Ion-Pairing Reagents and the Analyte Sequence on the Electrospray Desorption Process for Oligonucleotides.
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评估离子对试剂的物理化学参数与寡核苷酸电喷雾解吸过程中的分析物序列之间的相互作用。
DOI：
10.1007/s13361-017-1671-6
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发表时间：
2017-08
影响因子：
3.2
通讯作者：
Bartlett MG
中科院分区：
文献类型：
--
作者：
Basiri B;Murph MM;Bartlett MG
烷基胺广泛用作寡核苷酸 LC-MS 过程中的离子配对剂。除了更好的色谱分离之外，它们还有助于寡核苷酸离子解吸到气相中，导致电荷态减少并减少阳离子加合。然而，此类离子配对剂的选择对寡核苷酸的 MS 信号强度有相当大的影响，因为它们也会引起显着的离子抑制。有趣的是，最佳离子对试剂应根据具体情况进行选择，因为它们的选择很大程度上受到所研究的寡核苷酸序列的影响。尽管给分析方法的开发带来了重大的实际困难，但这种对电喷雾组合物的细微差别响应非常强烈的高度可变的系统为电喷雾电离过程的基础研究提供了极好的机会。我们使用该系统的研究定量揭示了影响寡核苷酸 ESI 电离效率的主要因素。离子对试剂的沸点、质子亲和力、分配系数、水溶性和亨利定律常数以及寡核苷酸的疏水性胸腺嘧啶含量等参数被发现是最重要的影响因素。这些参数的识别还允许开发统计预测算法，该算法可以帮助为每个特定的寡核苷酸序列选择最佳的 IP 试剂。我们相信，寡核苷酸生物分析领域的研究将显着受益于该算法（包含在补充材料中），因为它提倡对许多寡核苷酸序列使用鲜为人知但更合适的 TEA 离子对替代品。
Alkylamines are widely used as ion-pairing agents during LC-MS of oligonucleotides. In addition to a better chromatographic separation, they also assist with the desorption of oligonucleotide ions into the gas phase, cause charge state reduction and decrease cation adduction. However, the choice of such ion-pairing agents has considerable influence on the MS signal intensity of oligonucleotides as they can also cause significant ion suppression. Interestingly, optimal ion-pairing agents should be selected on a case by case basis as their choice is strongly influenced by the sequence of the oligonucleotide under investigation. Despite imposing major practical difficulties to analytical method development, such a highly variable system that responds very strongly to the nuances of the electrospray composition provides an excellent opportunity for a fundamental study of the electrospray ionization process. Our investigations using this system quantitatively revealed the major factors that influenced the ESI ionization efficiency of oligonucleotides. Parameters such as boiling point, proton affinity, partition coefficient, water solubility and Henry’s law constants for the ion-pairing reagents and the hydrophobic thymine content of the oligonucleotides were found to be the most significant contributors. Identification of these parameters also allowed for the development of a statistical predictive algorithm that can assist with the choice of an optimum IP agent for each particular oligonucleotide sequence. We believe that research in the field of oligonucleotide bioanalysis will significantly benefit from this algorithm (included in supplementary material) as it advocates for the use of lesser-known but more suitable ion-pair alternatives to TEA for many oligonucleotide sequences.
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影响因子：
7.4
作者：
Huffman, Brian A.;Poltash, Michael L.;Hughey, Christine A.
通讯作者：
Hughey, Christine A.
影响因子：
56.9
作者：
Berkenkamp, S;Kirpekar, F;Hillenkamp, F
通讯作者：
Hillenkamp, F
DOI：
10.1002/bms.1200230604
发表时间：
1994-06-01
期刊：
BIOLOGICAL MASS SPECTROMETRY
影响因子：
--
作者：
BLEICHER, K;BAYER, E
通讯作者：
BAYER, E
DOI：
10.1007/s13361-012-0509-5
发表时间：
2013-02-01
影响因子：
3.2
作者：
Chen, Buyun;Mason, Sadie F.;Bartlett, Michael G.
通讯作者：
Bartlett, Michael G.
影响因子：
7.4
作者：
Hogan, Christopher J., Jr.;Carroll, James A.;Rohrs, Henry W.;Biswas, Pratim;Gross, Michael L.
通讯作者：
Gross, Michael L.