气相中碱金属离子与丝氨酸、 亮氨酸和赖氨酸五肽复合物的裂解反应

doi:10.7503/cjcu20130721

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (1): 37.doi: 10.7503/cjcu20130721

气相中碱金属离子与丝氨酸、亮氨酸和赖氨酸五肽复合物的裂解反应

魏王慧¹, 王青¹, 储艳秋¹(), 汪日志²(), 丁传凡¹

1. 复旦大学化学系激光化学研究所, 上海 200433
2. Department of Material Engineering, University of British Columbia, Canada

收稿日期:2013-07-25 出版日期:2014-01-10 发布日期:2013-12-13
作者简介:联系人简介: 储艳秋, 男, 博士, 副教授, 主要从事质谱法研究有机分子和生物大分子及其相互作用的研究. E-mail:chuyq@fudan.edu.cn;汪日志, 男, 博士, 教授, 主要从事生物材料、生物力学和生物模拟等方面的研究. E-mail: rizhi9752@hotmail.com
基金资助:
国家科技支撑计划项目(批准号: 2009BAK60B03)、国家重大科学仪器设备开发专项项目(批准号: 2011YQ090005)和上海市分子催化和功能材料重点实验室高级访问学者基金(批准号: 13FG081)资助

Fragmentation Reactions of Complexes of Alkali Metal Ions with Pentaserine, Pentaleucine and Pentalysine in Gas Phase^†

WEI Wanghui¹, WANG Qing¹, CHU Yanqiu^1,^*(), WANG Rizhi^2,^*(), DING Chuanfan¹

1. Laser Chemistry Institute, Department of Chemistry, Fudan University, Shanghai 200433, China
2. Department of Materials Engineering, University of British Columbia, Canada

Received:2013-07-25 Online:2014-01-10 Published:2013-12-13
Contact: CHU Yanqiu,WANG Rizhi E-mail:chuyq@fudan.edu.cn;rizhi9752@hotmail.com
Supported by:
† Supported by the National Science and Technology Pillar Program of China(No.2009BAK60B03), the National Major Scientific Instrument, Equipment Development Project of China(No.2011YQ090005) and the Senior Visiting Scholar Foundation for Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Shanghai, China(No.13FG081)

摘要/Abstract

摘要：

为了探索金属离子对含有不同侧链的多肽气相解离的影响, 采用质谱法研究了碱金属离子Li⁺, Na⁺, K⁺, Rb⁺和Cs⁺分别与丝氨酸、亮氨酸和赖氨酸五肽(分别简写为S5, L5和K5)形成的复合物的裂解反应. 质谱定性结果表明, 5种碱金属离子均可以在气相中与丝氨酸、亮氨酸和赖氨酸五肽形成配合比为1∶1 和2∶1的非共价复合物; 竞争反应结果表明, 随着碱金属离子半径的增加, 它们与3种五肽的结合能力逐渐减弱. 质谱定量结果表明, K⁺与丝氨酸、亮氨酸和赖氨酸五肽复合物的结合常数分别为8.94×10⁴, 2.83×10⁴和2.50×10³ L/mol, 表明K⁺与五肽复合物的结合强度按照丝氨酸、亮氨酸和赖氨酸的顺序依次减小. 含不同侧链碱金属离子-五肽复合物的碰撞诱导解离结果表明, 复合物的碎裂主要发生在骨架上, 丝氨酸五肽复合物最易碎裂, 亮氨酸五肽复合物其次, 赖氨酸五肽复合物则较难碎裂, 且3种复合物的侧链断裂情况也呈现明显差异. 此外, 研究了Na⁺与亮氨酸五肽复合物所产生的碎片离子, 分析了不同离子之间的来源关系, 并以Dunbar的复合物理论模型为依据, 推测在碎裂过程中, 碱金属离子可能向五肽的碳端或氮端偏移. 质谱碎片分析结果表明, 在2∶1的非共价复合物中, 第一个碱金属离子与五肽上4个酰胺键的羰基结合, 第二个碱金属离子与五肽的羧基氧原子结合.

关键词: 质谱法, 碰撞诱导解离, 碱金属离子, 五肽, 裂解反应

Abstract:

For exploring the effects of alkali metal ions on the dissociations of peptides with different side chains in the gas phase, the complexes of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ with pentapeptides, Ser-Ser-Ser-Ser-Ser(S5), Leu-Leu-Leu-Leu-Leu(L5) and Lys-Lys-Lys-Lys-Lys(K5), were chosen to investigate the fragmentation reaction pathways by mass spectrometry. The experimental results indicated that alkali metal ions and S5, L5, K5 can form 1∶1 and 2∶1 non-covalent complexes in the gas phase, and the binding strength between alkali metal ions and pentapeptides descend with the increasing of the radii of alkali metal ions. Quantitative analyses of mass spectra demonstrated that the binding constants for the complexes of K⁺ with S5, L5 and K5 are 8.94×10⁴, 2.83×10⁴ and 2.50×10³ L/mol, respectively, revealing that the binding strength of complexes decrease in order of S5, L5 and K5. The analyses of the fragment ions arising from the complexes of alkali metal ions with pentapeptides showed that the dissociations mainly occur in the backbones of the peptides. Among three pentapeptides, the complexes of pentaserines are the easiest to fragment, pentaleucines take second place, while pentalysines are the hardest. The dissociations also occur in the side chains, and there are significant differences among the three complexes. Moreover, the relationships among various fragment ions arising from the complex of Na⁺ with L5 were tested. Based on the theoretical model of Dunbar, it was proposed that in the fragmentation process, the alkali metal ion may shift to the N- or C-terminal of the pentapeptide. In 2∶1 complex, the first alkali metal ion may conjugate to the carbonyl groups of four amides, while the second one may conjugate to the oxygen atoms of carboxyl group of the pentapeptide.

Key words: Mass spectrometry, Collision induced dissociation, Alkali metal ion, Pentapeptide, Fragmentation reaction

中图分类号:

O657

TrendMD:

魏王慧, 王青, 储艳秋, 汪日志, 丁传凡. 气相中碱金属离子与丝氨酸、亮氨酸和赖氨酸五肽复合物的裂解反应. 高等学校化学学报, 2014, 35(1): 37.

WEI Wanghui, WANG Qing, CHU Yanqiu, WANG Rizhi, DING Chuanfan. Fragmentation Reactions of Complexes of Alkali Metal Ions with Pentaserine, Pentaleucine and Pentalysine in Gas Phase^†. Chem. J. Chinese Universities, 2014, 35(1): 37.

图/表 12

Scheme 1 Nomenclature used for the fragments of pentapeptideR1=R2=R3=R4=R5=—H, —CH2OH, —CH2CH(CH3)2, —(CH2)4NH2.

Fig.1 Mass spectra for competition reaction of pentapeptides with alkali metal ions in a molar ratio of 1∶1∶1∶1∶1∶1∶1(A) G5; (B) S5; (C) L5; (D) K5. c(Pentapeptide)=c(Alkali metal ion)=1.0×10-4 mol/L.

Table 1 Ka1 values of the complexes of G5 with K+

10⁵ [G5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-5 K_a1/(L·mol^-1)
5.00	10.00	7.54	100.00	97.94	0.487	0.477	4.84
5.00	15.00	3.17	100.00	98.03	0.497	0.487	4.06
5.00	20.00	1.92	100.00	98.35	0.499	0.491	3.96
5.00	25.00	1.68	100.00	98.42	0.499	0.492	3.15
5.00	30.00	1.32	100.00	99.31	0.498	0.495	3.15
Average							3.83
SD							0.70
RSD(%)							18.2

Table 2 Ka1 values of the complexes of S5 with K+

10⁵ [S5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-4 $K a 1$ /(L·mol^-1)
5.00	10.00	23.99	100.00	51.09	0.571	0.292	9.86
5.00	15.00	12.80	100.00	70.47	0.546	0.384	9.25
5.00	20.00	8.15	100.00	97.10	0.487	0.473	9.49
5.00	25.00	6.97	100.00	97.57	0.489	0.477	8.09
5.00	30.00	5.47	100.00	98.15	0.491	0.482	8.00
Average							8.94
SD							0.84
RSD(%)							9.4

Table 2 Ka1 values of the complexes of S5 with K+

10⁵ [S5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-4 $K a 1$ /(L·mol^-1)
5.00	10.00	23.99	100.00	51.09	0.571	0.292	9.86
5.00	15.00	12.80	100.00	70.47	0.546	0.384	9.25
5.00	20.00	8.15	100.00	97.10	0.487	0.473	9.49
5.00	25.00	6.97	100.00	97.57	0.489	0.477	8.09
5.00	30.00	5.47	100.00	98.15	0.491	0.482	8.00
Average							8.94
SD							0.84
RSD(%)							9.4

Table 3 Ka1 values of the complexes of L5 with K+

10⁵ [L5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-4 $K a 1$ /(L·mol^-1)
5.00	10.00	51.03	100.00	8.19	0.628	0.051	3.08
5.00	15.00	33.63	100.00	13.53	0.680	0.092	2.79
5.00	20.00	21.85	100.00	15.31	0.729	0.112	3.01
5.00	25.00	18.68	100.00	17.09	0.737	0.126	2.68
5.00	30.00	15.71	100.00	20.75	0.733	0.152	2.57
Average							2.83
SD							0.21
RSD(%)							7.4

Table 3 Ka1 values of the complexes of L5 with K+

10⁵ [L5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-4 $K a 1$ /(L·mol^-1)
5.00	10.00	51.03	100.00	8.19	0.628	0.051	3.08
5.00	15.00	33.63	100.00	13.53	0.680	0.092	2.79
5.00	20.00	21.85	100.00	15.31	0.729	0.112	3.01
5.00	25.00	18.68	100.00	17.09	0.737	0.126	2.68
5.00	30.00	15.71	100.00	20.75	0.733	0.152	2.57
Average							2.83
SD							0.21
RSD(%)							7.4

Table 4 Ka1 values of the complexes of K5 with K+

10⁵ [K5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-3 $K a 1$ /(L·mol^-1)
5.00	10.00	100.00	22.88	7.29	0.176	0.056	2.68
5.00	15.00	100.00	34.33	14.11	0.231	0.095	2.66
5.00	20.00	100.00	42.90	22.47	0.259	0.136	2.47
5.00	25.00	100.00	51.93	31.90	0.282	0.174	2.37
5.00	30.00	100.00	61.13	40.60	0.303	0.201	2.31
Average							2.50
SD							0.17
RSD(%)							6.8

Table 4 Ka1 values of the complexes of K5 with K+

10⁵ [K5]₀/(mol·L^-1)	10⁵ [K⁺]₀/(mol·L^-1)	I_P	I_PM	I_PM2	a₁	a₂	10^-3 $K a 1$ /(L·mol^-1)
5.00	10.00	100.00	22.88	7.29	0.176	0.056	2.68
5.00	15.00	100.00	34.33	14.11	0.231	0.095	2.66
5.00	20.00	100.00	42.90	22.47	0.259	0.136	2.47
5.00	25.00	100.00	51.93	31.90	0.282	0.174	2.37
5.00	30.00	100.00	61.13	40.60	0.303	0.201	2.31
Average							2.50
SD							0.17
RSD(%)							6.8

Fig.2 Relationship between intensity of mass spectrometric peak and normalized collision energy The precursors are the complexes of G5(■), S5(●), L5(▲) or K5(◆) with H+(A), Li+(B) and 2Li+(C).

Fig.3 CID spectra for the precursor of [K5+Na]+ at different collision energies

Fig.4 CID breakdown curves for the complexes of Na+ with pentaleucinea. Precursor ion [L5+Na]+; b. [b4+Na+OH]+; c. [b4+Na-H]+; d. [y3+Na+H]+; e. [b3+Na-H]+; f. [y2+Na+H]+.

Table 5 Main fragment ions of protonated and alkali metal cationized S5 complexes obtained with CID

Precursor ion(#)	a_n/a_n^/a_n^*	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[S5+H]⁺	a₄, a₃, a₂, a₁, a₄-H₂O, a₄-2H₂O, a₃-H₂O, a₃-2H₂O, a₂-H₂O	b₄, b₃, b₂, b₄-H₂O, b₃-H₂O, b₂-H₂O, b₃-2H₂O	y₃, y₂, y₁	[#-H₂O]⁺, [#-2H₂O]⁺, [#-3H₂O]⁺, [#-4H₂O]⁺
[S5+Li]⁺	a₄^, a₄^-CH₂O, a₄^-H₂O, a₃^, a₃^-CH₂O, a₃^-H₂O, a₂^, a₂^-CH₂O, a₂^-H₂O, a₁^	[b₄+Li+OH]⁺, [b₄+Li+OH- CH₂O]⁺, b₄^-H₂O, b₄^-CO₂, [b₃+Li+OH]⁺, b₄^-H₂O-CH₂O, b₃^-H₂O, b₄^, b₃^-CO₂, [b₃+ Li+OH-CH₂O]⁺, b₃^, b₂^, b₃^-H₂O-CH₂O, b₂^-H₂O, b₂^*-H₂O-CH₂O	y₂^, y₂^-H₂O, y₁^*	[#-H₂O]⁺, [#-CH₂O]⁺, [#-H₂O-CH₂O]⁺ , [#-H₂O-CO₂]⁺, [#-H₂O-2CH₂O]⁺, [#-2H₂O-CH₂O]⁺
[S5+Na]⁺	a₄^, a₄^-CH₂O, a₃^, a₁^	[b₄+Na+OH]⁺, [b₄+Na+OH- CH₂O]⁺, b₄^, b₄^-H₂O, [b₃+ Na+OH]⁺, b₃^, b₂^, [b₃+Na+ OH-CH₂O]⁺	y₂^*	[#-H₂O]⁺, [#-CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-CO₂]⁺
[S5+K]⁺	a₄^, a₄^-CH₂O	[b₄+K+OH]⁺, [b₄+K+OH- CH₂O]⁺, b₄^, b₄^-H₂O, [b₃+ K+OH]⁺, [b₃+K+OH-CH₂O]⁺, b₃^*		K⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺
[S5+Rb]⁺				Rb⁺
[S5+Cs]⁺				Cs⁺
[S5+2Li-H]⁺	a₄^, a₃^, a₄^, a₃^	b₃^, b₃^-CH₂O, b₂^, b₂^-CH₂O	y₄^, y₃^, y₂^, y₁^, y₄^-CH₂O, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₄^-2CH₂O, y₃^-CH₂O	[#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-4CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-H₂O-3CH₂O]⁺, [#-2H₂O-3CH₂O]⁺
[S5+2Na-H]⁺	a₄^-CH₂O, a₄^-2CH₂O, a₄^-3CH₂O, a₃^-CH₂O	b₂^*, b₄^, b₄^*-CH₂O	y₄^, y₃^, y₂^, y₁^, y₄^-CH₂O, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₃^-2CH₂O, y₂^-2CH₂O	[#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#- 3CH₂O]⁺, [#-4CH₂O]⁺, [#-5CH₂O]⁺, [#-H₂O- CH₂O]⁺, [#-H₂O- 2CH₂O]⁺, [#-H₂O- 3CH₂O]⁺, [#-H₂O- 4CH₂O]⁺
[S5+2K-H]⁺	a₄^**-H₂O	b₃^-CH₂O, b₃^-2CH₂O, b₂^**-CH₂O	y₄^, y₃^, y₂^, y₁^, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₂^-2CH₂O	K⁺, [#-H₂O]⁺, [#-2H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-4CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-2H₂O- 2CH₂O]⁺, [#-H₂O- 3CH₂O]⁺, [#-2H₂O- 3CH₂O]⁺, [#-H₂O- 4CH₂O]⁺
[S5+2Rb-H]⁺	a₄^, a₄^-H₂O	b₃^, b₁^, b₃^**-2H₂O	y₄^, y₃^, y₂^, y₁^	Rb⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-H₂O- CH₂O]⁺, [#-H₂O-2CH₂O]⁺
[S5+2Cs-H]⁺	a₄^**-H₂O	b₃^**	y₄^, y₃^, y₁^, y₁^-CH₂O	Cs⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-3CH₂O]⁺

Table 5 Main fragment ions of protonated and alkali metal cationized S5 complexes obtained with CID

Precursor ion(#)	a_n/a_n^/a_n^*	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[S5+H]⁺	a₄, a₃, a₂, a₁, a₄-H₂O, a₄-2H₂O, a₃-H₂O, a₃-2H₂O, a₂-H₂O	b₄, b₃, b₂, b₄-H₂O, b₃-H₂O, b₂-H₂O, b₃-2H₂O	y₃, y₂, y₁	[#-H₂O]⁺, [#-2H₂O]⁺, [#-3H₂O]⁺, [#-4H₂O]⁺
[S5+Li]⁺	a₄^, a₄^-CH₂O, a₄^-H₂O, a₃^, a₃^-CH₂O, a₃^-H₂O, a₂^, a₂^-CH₂O, a₂^-H₂O, a₁^	[b₄+Li+OH]⁺, [b₄+Li+OH- CH₂O]⁺, b₄^-H₂O, b₄^-CO₂, [b₃+Li+OH]⁺, b₄^-H₂O-CH₂O, b₃^-H₂O, b₄^, b₃^-CO₂, [b₃+ Li+OH-CH₂O]⁺, b₃^, b₂^, b₃^-H₂O-CH₂O, b₂^-H₂O, b₂^*-H₂O-CH₂O	y₂^, y₂^-H₂O, y₁^*	[#-H₂O]⁺, [#-CH₂O]⁺, [#-H₂O-CH₂O]⁺ , [#-H₂O-CO₂]⁺, [#-H₂O-2CH₂O]⁺, [#-2H₂O-CH₂O]⁺
[S5+Na]⁺	a₄^, a₄^-CH₂O, a₃^, a₁^	[b₄+Na+OH]⁺, [b₄+Na+OH- CH₂O]⁺, b₄^, b₄^-H₂O, [b₃+ Na+OH]⁺, b₃^, b₂^, [b₃+Na+ OH-CH₂O]⁺	y₂^*	[#-H₂O]⁺, [#-CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-CO₂]⁺
[S5+K]⁺	a₄^, a₄^-CH₂O	[b₄+K+OH]⁺, [b₄+K+OH- CH₂O]⁺, b₄^, b₄^-H₂O, [b₃+ K+OH]⁺, [b₃+K+OH-CH₂O]⁺, b₃^*		K⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺
[S5+Rb]⁺				Rb⁺
[S5+Cs]⁺				Cs⁺
[S5+2Li-H]⁺	a₄^, a₃^, a₄^, a₃^	b₃^, b₃^-CH₂O, b₂^, b₂^-CH₂O	y₄^, y₃^, y₂^, y₁^, y₄^-CH₂O, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₄^-2CH₂O, y₃^-CH₂O	[#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-4CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-H₂O-3CH₂O]⁺, [#-2H₂O-3CH₂O]⁺
[S5+2Na-H]⁺	a₄^-CH₂O, a₄^-2CH₂O, a₄^-3CH₂O, a₃^-CH₂O	b₂^*, b₄^, b₄^*-CH₂O	y₄^, y₃^, y₂^, y₁^, y₄^-CH₂O, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₃^-2CH₂O, y₂^-2CH₂O	[#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#- 3CH₂O]⁺, [#-4CH₂O]⁺, [#-5CH₂O]⁺, [#-H₂O- CH₂O]⁺, [#-H₂O- 2CH₂O]⁺, [#-H₂O- 3CH₂O]⁺, [#-H₂O- 4CH₂O]⁺
[S5+2K-H]⁺	a₄^**-H₂O	b₃^-CH₂O, b₃^-2CH₂O, b₂^**-CH₂O	y₄^, y₃^, y₂^, y₁^, y₃^-CH₂O, y₂^-CH₂O, y₁^-CH₂O, y₂^-2CH₂O	K⁺, [#-H₂O]⁺, [#-2H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-4CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-2H₂O- 2CH₂O]⁺, [#-H₂O- 3CH₂O]⁺, [#-2H₂O- 3CH₂O]⁺, [#-H₂O- 4CH₂O]⁺
[S5+2Rb-H]⁺	a₄^, a₄^-H₂O	b₃^, b₁^, b₃^**-2H₂O	y₄^, y₃^, y₂^, y₁^	Rb⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-3CH₂O]⁺, [#-H₂O- CH₂O]⁺, [#-H₂O-2CH₂O]⁺
[S5+2Cs-H]⁺	a₄^**-H₂O	b₃^**	y₄^, y₃^, y₁^, y₁^-CH₂O	Cs⁺, [#-H₂O]⁺, [#-CH₂O]⁺, [#-2CH₂O]⁺, [#-H₂O-CH₂O]⁺, [#-H₂O-2CH₂O]⁺, [#-3CH₂O]⁺

Table 6 Main product ions of protonated and alkali metal cationized L5 complexes obtained with CID

Precursor ion(#)	a_n/ $a n $ / $a n *$	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[L5+H]⁺	a₄, a₂, a₁, a₄-NH₃, a₃-NH₃, a₄-CH₂-CH-(CH₃)₂	b₃, b₂	y₄, y₃, y₂	[#-H₂O]⁺
[L5+Li]⁺	a₄^, a₃^, a₃^-(CH₃)₂, a₄^- CH₂-CH-(CH₃)₂, a₂^, a₂^-(CH₃)₂	[b₄+Li+OH]⁺, b₄^-NH₃, [b₃+Li+OH]⁺, b₃^-NH₃, b₄^, b₃^, b₂^*	y₃^, y₂^, y₁^*	[#-H₂O-NH₃]⁺
[L5+Na]⁺	a₄^, a₃^, a₁^, a₃^-CH₂-CH- (CH₃)₂, a₂^*-CH₂-CH-(CH₃)₂	[b₄+Na+OH]⁺, b₃^, [b₃+Na+OH]⁺, b₂^	y₂^, y₁^
[L5+K]⁺	a₄^, a₃^	[b₄+K+OH]⁺, b₄^*, [b₃+K+OH]⁺	y₂^, y₂^-NH₃, y₄^*-CO	K⁺, [#-CO]⁺, [#-CO₂]⁺
[L5+Rb]⁺		[b₄+Rb+OH]⁺		Rb⁺
[L5+Cs]⁺				Cs⁺
[L5+2Li-H]⁺	a₄^, a₃^, a₄^, a₃^, a₁^, a₃^-CO₂, a₂^*-CO₂	b₂^, b₄^-H₂O-NH₃, b₃^*-H₂O-NH₃	y₄^, y₂^, y₁^*, y₃^, y₁^*	[#-CO₂]⁺, [#-H₂O-NH₃]⁺
[L5+2Na-H]⁺	a₄^*, a₄^, a₃^, a₂^, a₁^, a₃^-H₂O-NH₃, a₂^-H₂O-NH₃, a₂^-CH₂-CH-(CH₃)₂	b₃^, b₃^-NH₃	y₄^, y₃^, y₂^, y₁^, y₂^**-CO₂	[#-CO₂]⁺
[L5+2K-H]⁺	a₄^, a₃^, a₂^, a₁^-(CH₃)₂		y₄^, y₃^, y₂^, y₁^, y₁^**-H₂O-NH₃	K⁺
[L5+2Rb-H]⁺	a₃^-CH₂-CH-(CH₃)₂, a₂^-CH₂-CH-(CH₃)₂		y₃^, y₂^, y₁^, y₃^-NH₃	Rb⁺
[L5+2Cs-H]⁺	a₂^**-CH₂-CH-(CH₃)₂		y₃^, y₂^, y₁^, y₄^-CH₂-CH-(CH₃)₂	Cs⁺

Table 6 Main product ions of protonated and alkali metal cationized L5 complexes obtained with CID

Precursor ion(#)	a_n/ $a n $ / $a n *$	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[L5+H]⁺	a₄, a₂, a₁, a₄-NH₃, a₃-NH₃, a₄-CH₂-CH-(CH₃)₂	b₃, b₂	y₄, y₃, y₂	[#-H₂O]⁺
[L5+Li]⁺	a₄^, a₃^, a₃^-(CH₃)₂, a₄^- CH₂-CH-(CH₃)₂, a₂^, a₂^-(CH₃)₂	[b₄+Li+OH]⁺, b₄^-NH₃, [b₃+Li+OH]⁺, b₃^-NH₃, b₄^, b₃^, b₂^*	y₃^, y₂^, y₁^*	[#-H₂O-NH₃]⁺
[L5+Na]⁺	a₄^, a₃^, a₁^, a₃^-CH₂-CH- (CH₃)₂, a₂^*-CH₂-CH-(CH₃)₂	[b₄+Na+OH]⁺, b₃^, [b₃+Na+OH]⁺, b₂^	y₂^, y₁^
[L5+K]⁺	a₄^, a₃^	[b₄+K+OH]⁺, b₄^*, [b₃+K+OH]⁺	y₂^, y₂^-NH₃, y₄^*-CO	K⁺, [#-CO]⁺, [#-CO₂]⁺
[L5+Rb]⁺		[b₄+Rb+OH]⁺		Rb⁺
[L5+Cs]⁺				Cs⁺
[L5+2Li-H]⁺	a₄^, a₃^, a₄^, a₃^, a₁^, a₃^-CO₂, a₂^*-CO₂	b₂^, b₄^-H₂O-NH₃, b₃^*-H₂O-NH₃	y₄^, y₂^, y₁^*, y₃^, y₁^*	[#-CO₂]⁺, [#-H₂O-NH₃]⁺
[L5+2Na-H]⁺	a₄^*, a₄^, a₃^, a₂^, a₁^, a₃^-H₂O-NH₃, a₂^-H₂O-NH₃, a₂^-CH₂-CH-(CH₃)₂	b₃^, b₃^-NH₃	y₄^, y₃^, y₂^, y₁^, y₂^**-CO₂	[#-CO₂]⁺
[L5+2K-H]⁺	a₄^, a₃^, a₂^, a₁^-(CH₃)₂		y₄^, y₃^, y₂^, y₁^, y₁^**-H₂O-NH₃	K⁺
[L5+2Rb-H]⁺	a₃^-CH₂-CH-(CH₃)₂, a₂^-CH₂-CH-(CH₃)₂		y₃^, y₂^, y₁^, y₃^-NH₃	Rb⁺
[L5+2Cs-H]⁺	a₂^**-CH₂-CH-(CH₃)₂		y₃^, y₂^, y₁^, y₄^-CH₂-CH-(CH₃)₂	Cs⁺

Table 7 Main product ions of protonated and alkali metal cationized K5 complexes obtained with CID

Precursor ion(#)	a_n/ $a n $ / $a n *$	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[K5+H]⁺	a₄-(CH₂)₄-NH₂, a₃-(CH₂)₄-NH₂, a₁, a₁-NH₃	b₄, b₃, b₂, b₁, b₄-H₂O, b₃-H₂O, b₂-H₂O, b₄-H₂O-NH₃, b₄-H₂O-2NH₃, b₃-H₂O-NH₃, b₃-H₂O-2NH₃, b₂-H₂O-NH₃, b₂-H₂O-2NH₃	y₄, y₃, y₂, y₁	[#-H₂O]⁺
[K5+Li]⁺	a₁^, a₂^- (CH₂)₄-NH₂	[b₄+Li+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₄^-H₂O, b₄^-H₂O-NH₃, [b₃+Li+OH]⁺, b₃^-H₂O, b₃^-H₂O-NH₃, b₂^-H₂O, b₂^-H₂O-NH₃	y₂^, y₁^	[#-H₂O]⁺
[K5+Na]⁺	a₁^, a₃^- (CH₂)₄-NH₂	[b₄+Na+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₄^-H₂O, b₂^-H₂O-NH₃, [b₃+Na+OH]⁺, b₃^*-H₂O	y₄^-CO₂, y₂^, y₁^*	[#-H₂O]⁺
[K5+K]⁺	a₂^*	[b₄+K+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₃^-H₂O, b₂^-H₂O, [b₃+K+OH]⁺	y₂^, y₁^, y₁^*-(CH₂)₄	K⁺, [#-H₂O]⁺, [#-CO₂]⁺
[K5+Rb]⁺		[b₄+Rb+OH]⁺		Rb⁺
[K5+Cs]⁺		[b₄+Cs+OH]⁺		Cs⁺
[K5+2Li-H]⁺	a₄^, a₃^, a₂^, a₂^-H₂O-NH₃, a₁^*	b₃^, b₂^, b₄^, b₃^, b₁^*	y₄^, y₃^, y₂^, y₁^, y₄^, y₁^	[#-CO₂]⁺, [#-CO₂-CH₂-NH₂]⁺
[K5+2Na-H]⁺	a₄^, a₄^-4CH₂	b₄^, b₄^-CO₂, b₄^, b₃^, b₂^*	y₄^, y₃^, y₂^, y₁^, y₃^-CO₂, y₂^-CO₂, y₄^, y₃^, y₂^, y₁^, y₁^**-4CH₂	[#-CO₂]⁺
[K5+2K-H]⁺	a₂^, a₂^- (CH₂)₄-NH₂	b₄^*	y₄^, y₃^, y₂^, y₁^, y₄^, y₃^	K⁺, [#-CO₂]⁺
[K5+2Rb-H]⁺		b₄^*	y₃^, y₂^, y₁^*, y₃^	Rb⁺
[K5+2Cs-H]⁺		b₄^*	y₃^, y₂^, y₁^**	Cs⁺

Table 7 Main product ions of protonated and alkali metal cationized K5 complexes obtained with CID

Precursor ion(#)	a_n/ $a n $ / $a n *$	$b n$ / $b n $ / $b n *$	$y n$ / $y n $ / $y n *$	Other
[K5+H]⁺	a₄-(CH₂)₄-NH₂, a₃-(CH₂)₄-NH₂, a₁, a₁-NH₃	b₄, b₃, b₂, b₁, b₄-H₂O, b₃-H₂O, b₂-H₂O, b₄-H₂O-NH₃, b₄-H₂O-2NH₃, b₃-H₂O-NH₃, b₃-H₂O-2NH₃, b₂-H₂O-NH₃, b₂-H₂O-2NH₃	y₄, y₃, y₂, y₁	[#-H₂O]⁺
[K5+Li]⁺	a₁^, a₂^- (CH₂)₄-NH₂	[b₄+Li+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₄^-H₂O, b₄^-H₂O-NH₃, [b₃+Li+OH]⁺, b₃^-H₂O, b₃^-H₂O-NH₃, b₂^-H₂O, b₂^-H₂O-NH₃	y₂^, y₁^	[#-H₂O]⁺
[K5+Na]⁺	a₁^, a₃^- (CH₂)₄-NH₂	[b₄+Na+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₄^-H₂O, b₂^-H₂O-NH₃, [b₃+Na+OH]⁺, b₃^*-H₂O	y₄^-CO₂, y₂^, y₁^*	[#-H₂O]⁺
[K5+K]⁺	a₂^*	[b₄+K+OH]⁺, b₄^, b₃^, b₂^, b₁^, b₃^-H₂O, b₂^-H₂O, [b₃+K+OH]⁺	y₂^, y₁^, y₁^*-(CH₂)₄	K⁺, [#-H₂O]⁺, [#-CO₂]⁺
[K5+Rb]⁺		[b₄+Rb+OH]⁺		Rb⁺
[K5+Cs]⁺		[b₄+Cs+OH]⁺		Cs⁺
[K5+2Li-H]⁺	a₄^, a₃^, a₂^, a₂^-H₂O-NH₃, a₁^*	b₃^, b₂^, b₄^, b₃^, b₁^*	y₄^, y₃^, y₂^, y₁^, y₄^, y₁^	[#-CO₂]⁺, [#-CO₂-CH₂-NH₂]⁺
[K5+2Na-H]⁺	a₄^, a₄^-4CH₂	b₄^, b₄^-CO₂, b₄^, b₃^, b₂^*	y₄^, y₃^, y₂^, y₁^, y₃^-CO₂, y₂^-CO₂, y₄^, y₃^, y₂^, y₁^, y₁^**-4CH₂	[#-CO₂]⁺
[K5+2K-H]⁺	a₂^, a₂^- (CH₂)₄-NH₂	b₄^*	y₄^, y₃^, y₂^, y₁^, y₄^, y₃^	K⁺, [#-CO₂]⁺
[K5+2Rb-H]⁺		b₄^*	y₃^, y₂^, y₁^*, y₃^	Rb⁺
[K5+2Cs-H]⁺		b₄^*	y₃^, y₂^, y₁^**	Cs⁺

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气相中碱金属离子与丝氨酸、亮氨酸和赖氨酸五肽复合物的裂解反应

Fragmentation Reactions of Complexes of Alkali Metal Ions with Pentaserine, Pentaleucine and Pentalysine in Gas Phase^†

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气相中碱金属离子与丝氨酸、 亮氨酸和赖氨酸五肽复合物的裂解反应

Fragmentation Reactions of Complexes of Alkali Metal Ions with Pentaserine, Pentaleucine and Pentalysine in Gas Phase†

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气相中碱金属离子与丝氨酸、亮氨酸和赖氨酸五肽复合物的裂解反应

Fragmentation Reactions of Complexes of Alkali Metal Ions with Pentaserine, Pentaleucine and Pentalysine in Gas Phase^†