Ion-molecule reactions of 2-methoxyethanol with some amines, carboxylic acids and amino acids under chemical ionization conditions

2-Methoxyethanol chemical ionization of amines, carboxylic acids and amino acids has been found to produce numerous adduct ions. The most intense adduct ions for amines are [M + H](+) and [M + 77](+), for carboxylic acids [M + 27](+), [M + 59](+) and [M + 77](+), and for amino acids [M + H](+), [M + 13](+), [M + 27](+) and [M + 77](+). Either the adduct ion [M + H](+) or [M + 77](+) was the most abundant ion found for amino acids. The proton affinities of amino acids are noticed to control the formation of the [M + H](+) and [M + 77](+) ions. The relative abundance of [M + 13](+) and [M + 27](+) ions varied for different amino acids being most intense for phenylalanine and aspartic acid. Copyright 1999 John Wiley & Sons, Ltd.     

TOF-SIMS study of cystine and cholesterol stones

Two different human stones, cystine and cholesterol from the kidney and gall bladder, were examined by time-of-flight secondary ion mass spectrometry using Ga(+) primary ions as bombarding particles. The mass spectra of kidney stone were compared with those measured for the standard compounds, cystine and cysteine. Similar spectra were obtained for the stone and cystine. The most important identification was based on the existence of the protonated molecules [M + H](+) and deprotonated molecules [M-H](-). The presence of cystine salt was also revealed in the stone through the sodiated cystine [M + Na](+) and the associated fragments, which might be due to the patient treatment history. In the gallstone, the deprotonated molecules [M-H](+) of cholesterol along with relatively intense characteristic fragments [M-OH](+) were detected.     

Detection of melamine in infant formula and grain powder by surface-assisted laser desorption/ionization mass spectrometry

We have developed a method for the determination of melamine (MEL), ammeline (AMN), and ammelide (AMD) by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using gold nanoparticles (Au NPs). The major peaks for MEL, AMN, and AMD at m/z 127.07, 128.05, and 129.04 are assigned to the [MEL + H](+), [AMN + H](+), and [AMD + H](+) ions. Because the three tested compounds adsorb weakly onto the surfaces of the Au NPs through Au-N bonding, they can be easily concentrated from complex samples by applying a simple trapping/centrifugation process. The SALDI-MS method provides limits of detection of 5, 10, and 300 nM for MEL, AMN, and AMD, respectively, at a signal-to-noise ratio of 3. The signal variation for 150-shot average spectra of the three analytes within the same spot was 15%, and the batch-to-batch variation was 20%. We have validated the practicality of this approach by the analysis of these three analytes in infant formula and grain powder. This simple and rapid SALDI-MS approach holds great potential for screening of MEL in foods.     

Intramolecular proton transfers in stereoisomeric gas-phase ions and the kinetic nature of the protonation process upon chemical ionization

The isobutane chemical ionization (CI) mass spectra of cis- and trans-1-butyl-3- and -4-dimethylaminocyclohexanols and of their methyl ethers exhibit abundant [MH - H(2)O](+) and [MH - MeOH](+) ions respectively. On the other hand, only the MH(+) ions of the cis-isomers exhibit significant [MH - H(2)O](+) and [MH - MeOH](+) ions under collision-induced dissociation (CID) conditions. The non-occurrence of water and methanol elimination in the CID spectra of the trans-isomers indicates retention of the external proton at the dimethylamino group in the MH(+) ions that survive after leaving the ion source and the first quadrupole of the triple-stage quadrupole ion separating system, and the trans-orientation of the two basic sites does not allow proton transfer from the dimethylamino group to the hydroxyl or methoxyl. Such transfer is allowed in the cis-amino alcohols and amino ethers via internal hydrogen-bonded (proton-bridged) structures, resulting in the elimination of water and methanol from the surviving MH(+) ions of these particular stereoisomers upon CID. The abundant [MH - ROH](+) ions in the isobutane-CI mass spectra of the trans-isomers indicates protonation at both basic sites, affording two isomeric MH(+) ions in each case, one protonated at the dimethylamino group and the other at the less basic oxygen function. These results show that the isobutane-CI protonation of the amino ethers and amino alcohols is a kinetically controlled process, occurring competitively at both basic sites of the molecules, despite the large difference between their proton affinities ( approximately 25 and approximately 35 kcal mol(-1); 1 kcal = 4.184 kJ). Copyright 1999 John Wiley & Sons, Ltd.     

Ion/molecule reactions provide new evidence for the structure and origin of

Ion/molecule reactions leading to formation of the diagnostically useful [C(3)H(4)N](+) ion (m/z 54), from acetonitrile CI plasma, have been studied using a tandem quadrupole mass spectrometer. Evidence is presented to demonstrate that [C(3)H(4)N](+) is produced from an ion/molecule reaction between [C(2)H(2)N](+) (m/z 40) and neutral acetonitrile, via a [C(4)H(5)N(2)](+) (m/z 81) intermediate. Loss of HCN, where the H atom arises from neutral acetonitrile and the CN group from [C(2)H(2)N](+) (m/z 40), leads to the production of [C(3)H(4)N](+) (m/z 54). These results are consistent with a proposed concerted elimination of HCN, generating m/z 54 as a methylene vinylidene ammonium ion. Copyright 1999 John Wiley & Sons, Ltd.     

The ESI CAD fragmentations of protonated 2,4,6-tris(benzylamino)- and tris(benzyloxy)-1,3,5-triazines involve benzyl-benzyl interactions: a DFT study

The electrospray ionization collisionally activated dissociation (CAD) mass spectra of protonated 2,4,6-tris(benzylamino)-1,3,5-triazine (1) and 2,4,6-tris(benzyloxy)-1,3,5-triazine (6) show abundant product ion of m/z 181 (C(14) H(13)(+)). The likely structure for C(14) H(13)(+) is α-[2-methylphenyl]benzyl cation, indicating that one of the benzyl groups must migrate to another prior to dissociation of the protonated molecule. The collision energy is high for the 'N' analog (1) but low for the 'O' analog (6) indicating that the fragmentation processes of 1 requires high energy. The other major fragmentations are [M?+?H-toluene](+) and [M?+?H-benzene](+) for compounds 1 and 6, respectively. The protonated 2,4,6-tris(4-methylbenzylamino)-1,3,5-triazine (4) exhibits competitive eliminations of p-xylene and 3,6-dimethylenecyclohexa-1,4-diene. Moreover, protonated 2,4,6-tris(1-phenylethylamino)-1,3,5-triazine (5) dissociates via three successive losses of styrene. Density functional theory (DFT) calculations indicate that an ion/neutral complex (INC) between benzyl cation and the rest of the molecule is unstable, but the protonated molecules of 1 and 6 rearrange to an intermediate by the migration of a benzyl group to the ring 'N'. Subsequent shift of a second benzyl group generates an INC for the protonated molecule of 1 and its product ions can be explained from this intermediate. The shift of a second benzyl group to the ring carbon of the first benzyl group followed by an H-shift from ring carbon to 'O' generates the key intermediate for the formation of the ion of m/z 181 from the protonated molecule of 6. The proposed mechanisms are supported by high resolution mass spectrometry data, deuterium-labeling and CAD experiments combined with DFT calculations.     

Mass spectral study of substituted allyl aryl and allyl alkyl selenides and some analogous sulfides

The electron impact (EI) mass spectra of allyl aryl selenides showed abundant molecular ions and many fragment ions containing the selenium atom. alpha-Cleavage is the dominant process in the fragmentation of selenides, and cleavage product ions are characteristic of the substituents. In the case of 3-methyl allyl and related aryl selenides, characteristic delta-hydrogen migration to the selenium atom is observed. A McLafferty-type rearrangement is found in benzyl allyl selenides and substituted alkyl allyl selenides. The charge on the rearrangement products preferably remains on the fragments containing the phenyl group. The [M - SeH](+), [M - CH(3)](+) and [M - C(2)H(4)](+) ions are found only in the EI mass spectrum of allyl phenyl selenide, and are attributed to a Claisen rearrangement in the source of the mass spectrometer. All structurally informative fragmentation processes are supported by collision induced dissociation spectra of molecular ions. The fragmentation patterns found in methane chemical ionization (CI) spectra of the selenides were significantly different from those observed in EI. The EI and CI mass spectra of analogous sulfides showed similar behaviour to that observed in the corresponding selenides. Copyright 1999 John Wiley & Sons, Ltd.     

Analysis of sonolytic degradation products of azo dye Orange G using liquid chromatography-diode array detection-mass spectrometry

In this paper, seven new sonolytic degradation products of Orange G were found and identified using powerful analytical techniques such as liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS), tandem mass spectrometry (MS/MS), and liquid chromatography with diode-array detection (LC-DAD). Each technique provided complementary information for the degradation products identification. In order to resolve the MS and MS/MS spectra obtained, the separation conditions were optimized. Among them, Orange G was unambiguously identified based on its abundant [M-H](-) ion, [M+H](+) ion, ultra-violet and visible spectra, retention time, and tandem mass spectrometric analysis compared with an authentic standard. The seven new degradation products were tentatively identified based on ultra-violet and visible spectra, [M-H](-) ions, and tandem mass spectrometry. The neutral losses of SO(2), SO(3), N(2) and H(2)O for MS/MS spectra which appear to be characteristic of the negative ion mode were observed. Based on this by-product identification, a possible multi-step degradation scheme is proposed. The analysis results of degradation products reveal that the degradation mechanism proceeds via reductive cleavage of the azo linkage, as well as intermolecular dehydration and desulfonation due to the powerful oxidizing hydroxyl radicals as well as hydrogen radical.     

Dereplication of known pregnane glycosides and structural characterization of novel pregnanes in Marsdenia tenacissima by high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry

In the search for novel natural products in plants, particularly those with potential bioactivity, it is important to efficiently distinguish novel compounds from previously isolated, known compounds, a process known as dereplication. In this study, electrospray ionization-multiple stage tandem mass spectrometry (ESI-MS(n)) was used to study the behaviour of 12 pregnane glycosides and genins previously isolated from Marsdenia tenacissima, a traditional Chinese medicinal plant, as a basis for dereplication of compounds in a plant extract. In addition to [M + Na](+) and [M + NH(4)](+) ions, a characteristic [M-glycosyl + H](+) ion was observed in full-scan mode with in-source fragmentation. Sequential in-trap collision-induced dissociation of [M + Na](+) ions from 11,12-diesters revealed consistent preferred losses of substituents first from C-12, then from C-11, followed by losses of monosaccharide fragments from the C-3 tri- and tetrasaccharide substituents. A crude methanol extract of M. tenacissima stems was analysed using high-performance liquid chromatography coupled to ESI-MS. Several previously isolated pregnane glycosides were dereplicated, and the presence of an additional nine novel pregnane glycosides is predicted on the basis of the primary and fragment ions observed, including two with a previously unreported C(4)H(7)O C-11/C-12 substituent of pregnane glycosides. This study is the first report of prediction of the structures of novel pregnane glycosides in a crude plant extract by a combination of in-source fragmentation and in-trap collision-induced dissociation and supports the usefulness of LC-ESI-MS(n) not only for dereplication of active compounds in extracts of medicinal plants but also for detecting the presence of novel related compounds.     

5-乙酰(苯甲酰)基-4-芳基-3,4-二氢嘧啶-2(1H)-酮的质谱裂解规律

利用飞行时间质谱仪的高分辨本领和离子阱串联质谱技术研究了5乙酰(苯甲酰)基4芳基3,4二氢嘧啶2(1H)酮(1-5)的电子轰击质谱的裂解规律.将所有质谱离子的精确质量数据经OpenLynx软件导出其分子离子和碎片离子的元素组成.根据质谱裂解规律,主要质谱离子得到了归属,并经离子阱串联质谱技术加以证实.化合物1-3的质谱出现了丰度很强的分子离子峰,其中1和3的分子离子为基峰,证明此类化合物的结构相当稳定.但4和5的分子离子峰却很弱(相对丰度在4%以下),这是由于嘧啶环4位上的苯环分别含有强吸电子基团-NO2(在苯环的间位才有此效应)和-Cl(苯环的2和4位均含有氯)所致.化合物1-5的主要裂解包括:分子离子失去芳基形成丰度很高的阳离子(M-Ar)+;分子离子失去羰基形成中等强度的阳离子(M-RCO)+;分子离子失去氢原子所产生的(M-H)+峰,以及消除中性分子NH=C=X的嘧啶环破裂裂解.此外,所有化合物在低质量区都发现明显的苯基阳离子Ph+(m/z77).并且还提出个别化合物的几个额外裂解过程为:化合物4(分子中苯环的3位上含有硝基)出现的基峰(M-OH)+;化合物5(分子中苯环的2和4位上都含有氯原子)出现了的基峰(M-Cl)+;化合物3和5分别出现了m/z238(16%)和m/z241(29%)的特征离子峰,它们由相应的离子消除中性分子四员内酰胺生成查耳酮离子,该离子具有共轭大Π键而稳定存在.     

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MS(n)) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C(14)-C(19) fatty acids, some of which were monounsaturated. Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type. The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations. The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MS(n) spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS(2) spectra of [M + K](+) ions, it was established that all components have a C(15:0) fatty acid at the sn-2 position of the glycerol backbone and C(14)-C(19) acids at the sn-1 position of the glycerol backbone. Copyright 1999 John Wiley & Sons, Ltd.     

Differentiation of aminomethyl corrole isomers by mass spectrometry

Two new isomeric aminomethyl corrole derivatives of [5,10,15-tris(pentafluorophenyl)corrolato]gallium(III) were synthesized with pyridine (py) molecules as axial ligands. When investigated by electrospray ionization mass spectrometry, in the positive and the negative ion modes, these compounds showed an unusual gas-phase behavior that could be used for their differentiation. In the positive ion mode, the differentiation was achieved through the formation of diagnostic fragment ions formed from [M-py?+?H](+) precursors, by (CH(3) )(2) NH and HF losses. An unusual addition of water to the main fragment ions provides an alternative route for isomer identification. Semi-empirical calculations were performed to elucidate the structures and stabilities of the main ionic species formed in the positive ion mode. In the negative ion mode isomer discrimination is accomplished via the fragmentation of the methoxide adduct ions [M-py?+?CH(3) O](-) through (CH(3) )(2) N(.) and HF losses.     

Effect of nitro groups and alkyl chain length on the negative ion tandem mass spectra of alkyl 3-hydroxy-5-(4'-nitrophenoxy) and alkyl 3-hydroxy-5-(2', 4'-dinitrophenoxy) benzoates

Tandem mass spectrometric behaviour was studied for a small combinatorial library of alkyl 3-hydroxy-5-(4'-nitrophenoxy) benzoates (A1-A5) and alkyl 3-hydroxy-5-(2', 4'-dinitrophenoxy) benzoates (B1-B5). The spectra were recorded by negative ion electrospray low-energy collision induced dissociation (CID) tandem mass spectrometry. The product ion spectra of [M - H](-) of the benzoates A1-A5 are similar, as are those of benzoates B1-B5. However, the spectra of the B series compounds differ significantly from those of the A series owing to the second electron-withdrawing nitro substituent in the B compounds. In addition, the length of the alkyl chain has an effect on the fragmentation. However, both series of compounds exhibit an abundant nitrophenoxy ion formed by the loss of 3-hydroxybenzoate. This is at m/z 138 in A1-A5 and at m/z 183 in B1-B5. A precursor ion scan of the nitrophenoxy ion provides a rapid method to identify the synthesised compounds in this type of combinatorial mixture. Copyright 1999 John Wiley & Sons, Ltd.     

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Polystyrenes with various end groups were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). These end groups were obtained by termination of the active anionic group by sulfonate or chlorosilane derivatives. Characteristic end group fragments for each sulfonate derivative were observed. On the one hand, for PS capped by methyl sulfonate, or -(CH(2))(4)-O-SO(2)-CH(3), almost complete end group fragment is observed at m/z 95 and a [O-SO(2)-CH(3)](-) molecular structure. On the other hand, when PS is terminated by silyl methyl sulfonate, or -Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3), the most characteristic fragment in the fingerprint secondary ion mass spectrum is located at m/z 153 with [Si(CH(3))(2)-O-SO(2)-CH(3)](+) and the complete end group peak, [Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3)](+), at m/z 201, is absent. According to the molecular structure, characteristic end group secondary ions can be emitted as complete or rearranged fragments. Various silylalkyl alcohol or sulfonate functionalities are analyzed and fragmentation pathways are discussed. To our knowledge, this is the first time that such rearrangement at silyl functions has been observed and demonstrated in fingerprint secondary ion mass spectra. Copyright 1999 John Wiley & Sons, Ltd.     

Characteristic ion clusters as determinants for the identification of pyrrolizidine alkaloid N-oxides in pyrrolizidine alkaloid-containing natural products using HPLC-MS analysis

Pyrrolizidine alkaloid (PA)-containing plants are widely distributed in the world. PAs are hepatotoxic, affecting livestock and humans. PA N-oxides are often present together with PAs in plants and also exhibit hepatotoxicity but with less potency. HPLC-MS is generally used to analyze PA-containing herbs, although PA references are unavailable in most cases. However, to date, without reference standards, HPLC-MS methodology cannot distinguish PA N-oxides from PAs because they both produce the same characteristic ions in mass spectra. In the present study, the mass spectra of 10 PA N-oxides and the corresponding PAs were systemically investigated using HPLC-MS to define the characteristic mass fragment ions specific to PAs and PA N-oxides. Mass spectra of toxic retronecine-type PA N-oxides exhibited two characteristic ion clusters at m/z 118-120 and 136-138. These ion clusters were produced by three unique fragmentation pathways of PA N-oxides and were not found in their corresponding PAs. Similarly, the nontoxic platynecine-type PA N-oxides also fragmented via three similar pathways to form two characteristic ion clusters at m/z 120-122 and 138-140. Further application of using these characteristic ion clusters allowed successful and rapid identification of PAs and PA N-oxides in two PA-containing herbal plants. Our results demonstrated, for the first time, that these characteristic ion clusters are unique determinants to discriminate PA N-oxides from PAs even without the availability of reference samples. Our findings provide a novel and specific method to differentiate PA N-oxides from PAs in PA-containing natural products, which is crucial for the assessment of their intoxication.     

Charge and substituent effects on the stability of porphyrin/G-quadruplex adducts

The adduct ions of two tetramolecular G-quadruplexes formed from the d(TGGGGT) and d(TTGGGGGT) single strands with a group of cationic porphyrins, with different charges and substituents, and one neutral porphyrin, were investigated by ESI-MS and ESI-MS/MS in the negative ion mode. Formation of [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions (where Q = quadruplex, n = number of quartets minus 1, P = porphyrin and p(+) = 0,1,2,3,4) indicates that the porphyrins are bound outside the quadruplexes providing an additional stabilization to those structures. The fragmentation pathways of the [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions depend on the number of positive charges (p(+)) of the porphyrins and on the overall complex charge (z(-)), but do not show a significant dependence on the type of the substituent groups in the porphyrins. Formation of the 'unfilled' ions [Q + P(p+)-(z + p)H(+)](z-) predominates for porphyrins with a higher number of positive charges. Strand separation with the formation of [T + P(p+)-(z-2 + p)H(+)]((z-2)-) and (SS-2H(+))(2-) ions, where T = [d(TG(4)T)](3) and [d(T(2)G(5)T)](3) and SS = d(TG(4)T) and d(T(2)G(5)T) is only observed for the complexes with a higher overall negative charge. Porphyrin loss with the formation of [Q + nNH(4)(+)-(z + n)H(+)](z-) ions occurs predominantly for the neutral and monocharged porphyrins. The predominant formation of the 'unfilled' ions, [Q + P(p+)-(z + n)H(+)](z-), for porphyrins with a higher number of charges shows that these porphyrins can prevent strand separation and preserve, at least partially, the quadruplex structure.     

Laser Desorption Mass Spectrometry of Some Organic Acids

Abstract

Positive and negative ion laser desorption (LD) mass spectra of organic acids are characterized by the emission of the quasimolecular ions (M+H)⁺ and (M-H)^?. Generation of (M+H)⁺ ions is interpreted as evidence for the occurence of high pressure proton transfer reactions in LD. Fragment ions can be rationalized by loss of stable neutral molecules from quasimolecular ions although decomposition may also be occuring prior to ionization. Features unique to LD, including the detection of pyrolysis products along with ions characteristic of the sample, are discussed in terms of the internal energy distribution in the irradiated microvolume. Negative ion mass spectra of acids are dominated by (M-H)^?, while positive ion spectra contain abundant fragment ions, underlining the utility of detecting negative ions for acidic compounds.     

1，3-二甲基尿嘧啶二聚体的飞行时间质谱裂解规律研究

采用不同进样方式、不同电子轰击能量和不同反应气压力测定了1,3 二甲基尿嘧啶二聚体(DMUD) 的4个立体异构体A、B、C、D的化学电离(CI)和电子轰击电离(EI)飞行时间质谱.不同方式所测得的CI谱结 果一致,4个异构体出现了强度不同的准分子离子峰(m/z=281),由此推断它们结构之间的相对稳定性次序为: B(trans syn)>D(cis syn)>A(trans anti)>C(cis anti).这一结论被低能量(25eV)电子轰击的EI谱所证实, 并且与合成产物的比例相吻合.EI谱用任何方式测谱均不出现分子离子峰(m/z=280),而出现其单体离子(m/z =140)且为基峰。给出了DMUD的飞行时间质谱裂解途径,同时对CI谱的裂解碎片进行了细致的讨论.     

环丙烷衍生物在D2O离子体系中的H/D交换反应

在Ｄ２Ｏ化学反应气条件下环丙烷衍生物的Ｈ／Ｄ交换反应特性,发现了三种新的产物离子（Ｍ＋１）＾＋、（Ｍ＋２）＾＋和（Ｍ＋３）＾＋。应用碰撞诱导碎裂（ＣＩＤ）技术研究了这些离子的碎裂反应特性。实验结果表明三种新的产物离子是由反应物与试剂离子间发生Ｈ／Ｄ交换反应生成的。并获得了环丙烷衍生物结构中活泼氢位置及其数量的信息。     

Fragmentation Study of Globularin Through Positive and Negative ESI/MS,CID/MS,and Tandem MS/MS

Abstract

The structure of globularin was studied by a mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision‐induced dissociation (CID), and tandem mass spectrometry. The mass spectrometry investigation was achieved through in‐source fragmentation of the deprotonated [M?H]^?, protonated [M+H]⁺, lithiated [M+Li]⁺, sodiated [M+Na]⁺, and potassium‐cationized [M+K]⁺ ions. This allowed collision‐induced dissociation spectra of the ionized molecular ions to be obtained to give valuable structural information regarding the nature of both the glycoside and the aglycone moieties and the effect of metal cationization on the CID spectra. Glycosidic fission and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during collision‐induced dissociation, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. Alkali metal cationization offers additional fragmentation pathways involving cross rings cleavage under CID conditions. Unlike the dissociation of protonated molecular ions, that of metal‐cationized molecules also provides sugar fragments where the C₀ ⁺ fragment corresponding with the glucose ion was obtained as a major daughter peak for all the studied compounds. Even with low abundance, fragment ions coordinated to K⁺ were also observed from [M+K]⁺.