193 nm Ultraviolet Photodissociation of Deprotonated Sialylated Oligosaccharides
193 nm Ultraviolet Photodissociation of Deprotonated Sialylated Oligosaccharides
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DOI：
10.1021/ac201751u
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发表时间：
2011-11-01
影响因子：
7.4
通讯作者：
Brodbelt, Jennifer S.
中科院分区：
文献类型：
--
作者：
Ko, Byoung Joon;Brodbelt, Jennifer S.
在线性离子阱中碰撞诱导解离（CID）和193 nm紫外光解离（UVPD）后获得的胎球蛋白的去质子化唾液酸化寡糖和聚糖的碎片模式。UVPD产生了一系列更广泛的跨环裂解离子，如A-和X-型离子，以及双裂解内离子，包括A/Y和X/B碎片离子。此外，UVPD产生独特的碎片离子所产生的唾液酸残基的三醇取代基的位点特异性裂解。相比之下，CID产生更常规的糖苷裂解和相对较少的A型离子。UVPD的双去质子化的唾液酸化低聚糖产生的大多是单去质子化的碎片离子，而在CID光谱的产物离子绝大多数是双电荷离子，结果归因于更广泛的裂解唾液酸残基UVPD和产品从电子光剥离。相对于CID，193 nm UVPD产生的产物离子阵列更大，包括由广泛的交叉环裂解和双裂解离子产生的产物离子，为聚糖的鉴别提供了更大的置信度。UVPD的几个关键位点特异性裂解，如涉及唾液酸部分的裂解，提供了聚糖组成的证据。
The fragmentation patterns of deprotonated sialylated oligosaccharides and glycans from fetuin obtained upon collisionally induced dissociation (CID) and 193 nm ultraviolet photodissociation (UVPD) in a linear ion trap are presented. UVPD produced a more extensive series of cross-ring cleavage ions, such as A- and X-type ions, and dual-cleavage internal ions, including A/Y and X/B fragment ions. In addition, UVPD generated unique fragment ions which arise from site-specific cleavage of the triol substituent of the sialic acid residue. In contrast, CID produced more conventional glycosidic cleavages and relatively few A-type ions. UVPD of doubly deprotonated sialylated oligosaccharides produced mostly singly deprotonated fragment ions, whereas the product ions in the CID spectra were overwhelmingly doubly charged ions, an outcome attributed to the more extensive cleavages of sialic acid residues upon UVPD and products from electron photodetachment. The larger array of product ions, including those arising from extensive cross-ring cleavages and dual-cleavage ions, generated by 193 nm UVPD relative to CID gives greater confidence for identification of glycans. Several key site-specific cleavages by UVPD, such as ones involving the sialic acid moieties, provide evidence of glycan composition.