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1.
报道了3种含双官能团苯基醚化合物2-(2,6-二氯苯氧基)丙腈,N-羟基-4-丁基苯乙酰胺,2-(1-甲基乙氧基)苯酚甲氨基酸甲酸酯的电子轰击质谱破裂,用亚稳分析和低能碰撞诱导解离子研究了3种化合物的分子离子碎裂规律,除简单的直接键断裂外,还证实经历了离子/中性(碎片)复合物中间体的单分子解离反应同时存在的竞争机理,解释了观察到分子内单氢迁移,双氢迁移现象。 相似文献
2.
2—羟基—4—邻苯二甲酰亚胺基丁酸的氢迁移反应 总被引:1,自引:0,他引:1
在甲烷为反应气的化学电离质谱条件下,质子化的2-羟基-4-邻苯二甲酰亚胺基丁酸的单分子质谱碎裂产生了m/z148的碎片离子,表明其碎裂过程发生了氢迁移反应,AM在分子轨道的理论计算结果为可能的质子化位置提供了理论依据;建立在氘代同位素标记和碰撞诱导解离实验的基础上,我们提出此离子的形成可能同时存在单氢迁移和双氢迁移,一些质谱图中的物征碎片中离子为可能的McLafferty重排和离子/中性(碎片)复 相似文献
3.
报道了丙硫咪唑(5-丙硫基-苯并咪唑-2氨基甲酸酯)的电子轰击质谱。利用串联质谱的低能碰撞诱导解离(CID)技术研究了此化合物的单分子解离,并提出了可能的离子/中性碎片复合筘间体碎裂机理,用来解释在质谱碎裂过程中出现的氢迁移(尤其是远距离的氢迁移)现象。 相似文献
4.
利用质量分析离子动能谱和碰撞诱导解离技采研究了邻、间、对二甲苯分子在电子轰击质谱中产生的双电荷离子[C8H10]2+、[C8H9]2+和单电荷离子[C8H10]+。根据测定的电荷分离反应的释放动能T和由此估算的双电荷离子电荷分离反应过渡态两电荷间距R,推测出过渡态的结构,利用单电荷离子[C8H10]+的MIKES/CID谱可区分邻二甲苯与间、对二甲苯异构体. 相似文献
5.
本文利用质量分析离子动能谱(MIKES)、碰撞诱导解离(CID)技术和电子捕获诱导解离(ECID)技术, 研究了邻、间、对苯二酚分子在电子轰击质谱(EIMS)中产生的双电荷离子[C6H6O2]^2^+, [C6H4O]^2^+和单电荷离子[C6H6O2]^+。根据测定的电荷分离反应动能释放值T和由此计算出的两电荷间距R, 推测出过渡态的结构。有趣的是, 可利用单电荷离子[C6H6O2]^+的MIKES/CID谱区分苯二酚异构体。 相似文献
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应用碰撞诱导解离技术研究了苯自身化学电离条件下和苯化学电离(甲苯为反应气)条件下离子-分子反应产物m/z155和156离子的碰撞诱导解离(CID)破裂特性,并与化学电离条件下质子化联苯生成m/z155离子的CID碎裂反应相比较,获得了苯离子1-分子反应产物m/z155和156离子的结构信息。 相似文献
10.
采用负离子模式的电喷雾傅立叶变换离子回旋共振质谱(ESI-FTICR-MS)对3个合成的肝素类化合物DHα、THα和THβ进行了全扫描一级谱和持续非共振辐照碰撞诱导解离(SORI-CID)串联质谱分析。样品浓度10μmol/L,流动泵注射直接进样。化合物中的磺酸胺和磺酸酯结构容易在一般电喷雾条件下发生分解,失去一个或者多个SO3,一级全扫描谱图中得到的谱峰均是带有单电荷或者双电荷的准分子离子峰。在串联质谱中,部分双电荷离子发生解离时,其二级谱图中子离子由单电荷子离子和双电荷子离子共同组成。通过对谱峰的局部放大,利用同位素峰的峰间距,能直接给出子离子的带电荷情况。同时,结合FTICRMS提供的高质量精度质谱数据,能够对所选取母离子的碎裂途径进行确认。离子质荷比测量的平均误差小于3.0×10-6。为结构复杂的类肝素化合物的质谱分析提供了借鉴。 相似文献
11.
詹东亮 《高等学校化学学报》1993,14(9):1270-1274
借助质量分析离子动能谱和串联质谱研究了由电子轰击产生的双电荷离子的单分子亚稳碎裂及碰撞诱导分解过程,讨论了两种实验方法导致的差别因素.此外,根据质量分析离子动能谱提供的双电荷离子电荷分离反应的动能释放值计算了两电荷中心间距的最小值,以判别按不同电荷分离方式碎裂的双电荷离子的过渡态结构. 相似文献
12.
Comparative MS/MS studies of singly and doubly charged electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) precursor peptide ions are described. The spectra from these experiments have been evaluated with particular emphasis on the data quality for subsequent data processing and protein/amino acid sequence identification. It is shown that, once peptide ions are formed by ESI or MALDI, their charge state, as well as the collision energy, is the main parameter determining the quality of collision-induced dissociation (CID) MS/MS fragmentation spectra of a given peptide. CID-MS/MS spectra of singly charged peptides obtained on a hybrid quadrupole orthogonal time-of-flight mass spectrometer resemble very closely spectra obtained by matrix-assisted laser desorption/ionization post-source decay time-of-flight mass spectrometry (MALDI-PSD-TOFMS). On the other hand, comparison of CID-MS/MS spectra of either singly or doubly charged ion species shows no dependence on whether ions have been formed by ESI or MALDI. This observation confirms that, at the time of precursor ion selection, further mass analysis is effectively decoupled from the desorption/ionization event. Since MALDI ions are predominantly formed as singly charged species and ESI ions as doubly charged, the associated difference in the spectral quality of MS/MS spectra as described here imposes direct consequences on data processing, database searching using ion fragmentation data, and de novo sequencing when ionization techniques are changed. 相似文献
13.
Electron-transfer dissociation (ETD) is a useful peptide fragmentation technique that can be applied to investigate post-translational
modifications (PTMs), the sequencing of highly hydrophilic peptides, and the identification of large peptides and even intact
proteins. In contrast to traditional fragmentation methods, such as collision-induced dissociation (CID), ETD produces c-
and z·-type product ions by randomly cleaving the N–Cα bonds. The disappointing fragmentation efficiency of ETD for doubly charged
peptides and phosphopeptide ions has been improved by ETcaD (supplemental activation). However, the ETD data derived from
most database search algorithms yield low confidence scores due to the presence of unreacted precursors and charge-reduced
ions within MS/MS spectra. In this work, we demonstrate that eight out of ten standard doubly charged peptides and phosphopeptides
can be effortlessly identified by electron-transfer coupled with collision-induced dissociation (ET/CID) using the SEQUEST
algorithm without further spectral processing. ET/CID was performed with the further dissociation of the charge-reduced ions
isolated from ETD ion/ion reactions. ET/CID had high fragmentation efficiency, which elevated the confidence scores of doubly
charged peptide and phosphospeptide sequencing. ET/CID was found to be an effective fragmentation strategy in “bottom-up”
proteomic analysis. 相似文献
14.
Ivan Haller Urooj A. Mirza Brian T. Chait 《Journal of the American Society for Mass Spectrometry》1996,7(7):677-681
Collision-induced dissociation product ion spectra of a series of doubly charged tryptic peptide ions produced by electrospray ionization were obtained by triple-quadrupole tandem mass spectrometry. The sequence information content of the product ion spectra was explored as a function of collision energy and collision-cell gas pressure for parent ions with molecular masses ranging from 300 to 2000 u. The energy range (at a given pressure) in which the degree of fragmentation is acceptable was found to be narrow for parent ions of a given mass, and the optimal collision energy was observed to exhibit a strong linear correlation with parent ion mass. This observed correlation opens the way for on-line software-controled selection of optimal mass spectrometric conditions in the enzymatic digestion-liquid chromatography-tandem mass spectrometric strategy of amino acid sequencing of proteins. 相似文献
15.
Joly N Vaillant C Cohen AM Martin P El Essassi M Massoui M Banoub J 《Rapid communications in mass spectrometry : RCM》2007,21(6):1062-1074
Electrospray ionization quadrupole time-of-flight (ESI-QqToF) mass spectra of the zwitteronic salts naloxonazine dihydrochloride 1 and naloxone hydrochloride 2, a common series of morphine opiate receptor antagonists, were recorded using different declustering potentials. The singly charged ion [M+H-2HCl](+) at m/z 651.3170 and the doubly charged ion [M+2H-2HCl](2+) at m/z 326.1700 were noted for naloxonazine dihydrochloride 1; and the singly charged ion [M+H-HCl](+) at m/z 328.1541 was observed for naloxone hydrochloride 2. Low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) experiments established the fragmentation routes of these compounds. In addition to the characteristic diagnostic product ions obtained, we noticed the formation of a series of radical product ions for the zwitteronic compounds 1 and 2, and also the formation of a distonic ion product formed from the singly charged ion [M+H-HCl](+) of naloxone hydrochloride 2. Confirmation of the various established fragmentation routes was effected by conducting a series of ESI-CID-QqTof-MS/MS product ion scans, which were initiated by CID in the atmospheric pressure/vacuum interface using a higher declustering potential. Deuterium labeling was also performed on the zwitteronic salts 1 and 2, in which the hydrogen atoms of the OH and NH groups were exchanged with deuterium atoms. Low-energy CID-QqTof-MS/MS product ion scans of the singly charged and doubly charged deuteriated molecules confirmed the initial fragmentation patterns proposed for the protonated molecules. Precursor ion scan analyses were also performed with a conventional quadrupole-hexapole-quadrupole tandem mass spectrometer and allowed the confirmation of the genesis of some diagnostic ions. 相似文献
16.
Nasioudis A Heeren RM van Doormalen I de Wijs-Rot N van den Brink OF 《Journal of the American Society for Mass Spectrometry》2011,22(5):837-844
Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming
low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions
of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole
ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid
mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of
substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially
the amine’s degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted
in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information
about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the
ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was
cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium
cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high
molar mass polyethers. 相似文献
17.
Lemoine J Tabarin T Antoine R Broyer M Dugourd P 《Rapid communications in mass spectrometry : RCM》2006,20(3):507-511
Protonated precursor ions of phosphorylated peptides containing a tyrosyl residue have been subjected to UV laser-induced dissociation (LID) at a wavelength of 220 nm and to collision-induced dissociation (CID) in an ion trap. As expected, neutral loss of the phosphate group is one of the predominant fragmentation channels during CID together with H2O elimination. In contrast, LID leads mainly to the homolytic cleavage of the tyrosyl side chain and a restrained loss of the phosphate group. Interestingly, the intensity of the dephosphorylated fragment ion is greatly minimized when CID is carried out next on the radical precursor ion of the singly and doubly charged species. 相似文献
18.
Kevin M. Downard Klaus Biemann 《Journal of the American Society for Mass Spectrometry》1994,5(11):966-975
The effect that charge state has on the collision-induced dissociation (CID) of peptide ions is examined in detail for several representative peptides under high-energy collision conditions. The CID spectra of singly and doubly charged precursor ions (generated by fast-atom bombardment and electrospray ionization, respectively) are compared for several peptides with similar primary structure. It is shown that for peptides that contain highly basic amino acids, the dissociation of doubly charged ions is strongly influenced by the position of these residues within the peptide and the general observations reported concerning the dissociation of singly charged ions can be extended to precursors with higher charge states. Based on the dissociation behavior of the doubly charged ions of these peptides, it is demonstrated that two charges can reside in close proximity in the precursor ions, overcoming possible repulsion effects, when favored by a high concentration of basic sites. In addition)’ this work illustrates that in the case of doubly charged ions..the charge state of some fragment ions can be determined directly from the mass-to-charge ratio assignments of the CID spectrum. 相似文献
19.
The combination of deprotonation (via ion/molecule and ion/ion reactions) and low-energy collision-induced dissociation (CID) has been explored for the enhanced characterisation of tryptic peptides via access to different precursor charge states. This approach allows instant access to fragmentation properties of singly and doubly protonated precursors (arising from the availability of mobile protons) in a single experiment. Considering both charge states extended our base of structurally informative data (in comparison with considering just a single charge state) due to generation of additional sequence ions and by obtaining supplementary structural information derived from selective cleavages. Roughly 37% of combined data sets (CID spectra of doubly and singly charged precursor) showed a greater database identification confidence than each set alone. Moreover, comparison between a number of sequence ions of the singly charged precursor and the doubly charged precursor provided a mean of distinguishing the two classes of tryptic peptides (arginine or lysine containing). 相似文献
20.
Liquid secondary ion mass spectrometry (L-SIMS) of six new functionalized macrocycles was investigated. All six compounds yielded abundant fragment ions and protonation molecular ions [M + H](+) under L-SIMS conditions. The proposed fragmentation mechanisms were supported by high-resolution accurate mass data from Fourier transform ion cyclotron resonance mass spectrometric and MS(n) experiments on using sustained off-resonance irradiation collision-induced dissociation. 相似文献