Formation of peptide aggregates during ESI: Size, charge, composition, and contributions to noise

Formation of peptide aggregates during ESI: Size, charge, composition, and contributions to noise
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DOI:
10.1016/s1044-0305(01)00283-5
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发表时间:
2001-09-01
影响因子:
3.2
通讯作者:
Clemmer, DE
Clemmer, DE
中科院分区:
化学3区
文献类型:
--
作者:
Counterman, AE;Hilderbrand, AE;Clemmer, DE

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离子迁移率/飞行时间技术已被用来研究Gly-xxx(其中xxxx=丙氨酸、天冬氨酸、天冬氨酸、谷氨酰胺、谷氨酸、组氨酸、亮氨酸、丝氨酸、苏氨酸和色氨酸)二肽模型体系中聚集的开始。在所采用的实验条件下,有证据表明,这些二肽的简单二元和四元混合物产生包含多达16到75个肽单位(和1到7个电荷)的簇。在一些体系中,簇组成似乎主要来自于肽单元的统计关联;其他二肽混合物(通常对于小簇)显示了非统计行为的证据,这可能是由于气相或溶液热化学中的一些差异引起的。最小聚集尺寸似乎在很大程度上取决于电荷状态。在z=2、3和4的电荷态族中,聚集体形成的平均阈值分别出现在类似于500、660和875的m/z处。我们简要地考虑了在电喷雾电离(ESI)中形成的聚集体可能有助于在复杂多肽混合物的分析中观察到的背景信号的想法。(C)2001年美国质谱学学会。
Ion mobility/time-of-flight techniques have been used to examine the onset of aggregation in model systems of Gly-Xxx (where Xxxx = Ala, Asn, Asp, Gln, Glu, His, Leu, Ser, Thr, and Trp) dipeptides. Under the experimental conditions employed, there is evidence that simple binary and quaternary mixtures of these dipeptides produce clusters containing as many as 16 to 75 peptide units (and 1 to 7 charges). In some systems, cluster compositions appear to come about largely from statistical association of peptide units; other dipeptide mixtures (and generally for small clusters) show evidence for nonstatistical behavior which could arise from some differences in gas-phase or solution thermochemistry. The minimum aggregate size appears to be largely determined by the charge state. Average thresholds for aggregate formation in the z = 2, 3, and 4 charge state families occur at m/z similar to 500, 660, and 875, respectively. We briefly consider the idea that aggregates formed during electrospray ionization (ESI) may contribute to the background signal observed in the analysis of complex peptide mixtures. (C) 2001 American Society for Mass Spectrometry.