Ultraviolet Photodissociation Spectra Research Articles

Structural characterization of wax esters using ultraviolet photodissociation mass spectrometry

Wax esters play critical roles in biological systems, serving functions from energy storage to chemical signaling. Their diversity is attributed to variations in alcohol and acyl chains, including their length, branching, and the stereochemistry of double bonds. Traditional analysis by mass spectrometry with collisional activations (CID, HCD) offers insights into acyl chain lengths and unsaturation level. Still, it falls short in pinpointing more nuanced structural features like the position of double bonds. As a solution, this study explores the application of 213-nm ultraviolet photodissociation (UVPD) for the detailed structural analysis of wax esters. It is shown that lithium adducts provide unique fragments as a result of Norrish and Norrish-Yang reactions at the ester moieties and photoinduced cleavages of double bonds. The product ions are useful for determining chain lengths and localizing double bonds. UVPD spectra of various wax esters are presented systematically, and the effect of activation time is discussed. The applicability of tandem mass spectrometry with UVPD is demonstrated for wax esters from natural sources. The UHPLC analysis of jojoba oil proves the compatibility of MS2 UVPD with the chromatography time scale, and a direct infusion is used to analyze wax esters from vernix caseosa. Data shows the potential of UVPD and its combination with CID or HCD in advancing our understanding of wax ester structures.Graphical

Observation of the Infrared-Induced Structural Change in the Microscopic Hydrogen Bond Network of Phenol-Methanol Cluster Cations in a Cold-Ion Trap.

To gain insight into microscopic hydrogen bond networks, we measured ultraviolet photodissociation (UVPD) spectra of the phenol-methanol 1:3 cluster cation, [PhOH(MeOH)3]+ trapped in a variable temperature ion trap. At low temperatures, an isomer with a ring-type hydrogen bond structure dominates, whereas at higher temperatures the chain-type isomers become dominant due to the flexibility of their hydrogen bond structures. We also found a clear temperature dependence of the spectral features, such as band position and width. In addition to the above measurement, we observed the infrared (IR) induced isomerization of [PhOH(MeOH)3]+ to study the dynamical aspects of hydrogen bond networks. We succeeded in observing IR-induced isomerization from the ring to chain forms of [PhOH(MeOH)3]+ at low temperature. The isomerization was clearly identified as a change in the UVPD spectra. The time evolution of the UVPD spectra after IR excitation indicated that the IR-induced isomerization occurs within a nanosecond. The chain-type isomers produced by the IR-induced isomerization are then converted back to the ring-type form by collisions with cold He buffer gas in the trap. This backward isomerization proceeds with a time constant of 100 μs under our experimental conditions. In this study, we evaluated the temperatures of the chain isomers during the backward isomerization on the basis of the spectral features.

Vibrational and electronic spectra of protonated vanillin: exploring protonation sites and isomerisation.

Photofragmentation spectra of protonated vanillin produced under electrospray ionisation (ESI) conditions have been recorded in the 3000-3700 cm-1 (vibrational) and 225-460 nm (electronic) ranges, using room temperature IRMPD (infrared multiphoton dissociation) and cryogenic UVPD (ultraviolet photodissociation) spectroscopies, respectively. The cold (∼50 K) electronic UVPD spectrum exhibits very well resolved vibrational structure for the S1 ← S0 and S3 ← S0 transitions, suggesting long excited state dynamics, similar to its simplest analogue, protonated benzaldehyde. The experimental data were combined with theoretical calculations to determine the protonation site and configurational isomer observed in the experiments.

D-Amino acid recognition of tripeptides studied by ultraviolet photodissociation spectroscopy of hydrogen-bonded clusters.

To understand the roles of D-amino acids, evaluating their chemical properties in living organisms is essential. Herein, D-amino acid recognition of peptides was investigated using a tandem mass spectrometer equipped with an electrospray ionization source and a cold ion trap. Ultraviolet (UV) photodissociation spectroscopy and water adsorption of hydrogen-bonded protonated clusters of tryptophan (Trp) enantiomers and tripeptides (SAA, ASA, and AAS, where S and A denote L-serine and L-alanine, respectively) were carried out at 8K in the gas phase. In the UV photodissociation spectrum of H+(D-Trp)ASA, the bandwidth of the S1-S0 transition, which corresponds to the ππ* state of the Trp indole ring, was narrower than those of the other five clusters, H+(D-Trp)SAA, H+(D-Trp)AAS, H+(L-Trp)SAA, H+(L-Trp)ASA, and H+(L-Trp)AAS. In the UV photoexcitation of H+(D-Trp)ASA(H2O)n, which were formed via water adsorption on gas-phase H+(D-Trp)ASA, the evaporation of water molecules was the main photodissociation pathway. An NH2CHCOOH-eliminated ion and H+ASA were observed in the product ion spectrum. By contrast, water molecules adsorbed on the other five clusters remained on the product ions for NH2CHCOOH elimination and Trp detachment after the UV photoexcitation. The results indicated that the indole ring of Trp was located on the surface of H+(D-Trp)ASA, and the amino and carboxyl groups of Trp formed hydrogen bonds in H+(D-Trp)ASA. For the other five clusters, the indole rings of Trp were hydrogen bonded in the clusters, and the amino and carboxyl groups of Trp were present on the cluster surfaces.

Electronic Interaction between Aromatic Chromophores in Dibenzo-Crown Ether Complexes with Alkali Metal Ions Investigated via Cold Gas-Phase Spectroscopy

This study investigated the geometric and electronic structures of dibenzo-21-crown-7 (DB21C7) and dibenzo-24-crown-8 (DB24C8) complexes with alkali metal ions, identified as M+(DB21C7) and M+(DB24C8) (M = Na, K, Rb, and Cs), respectively. We observed the ultraviolet photodissociation (UVPD) spectra of these complexes under cold (∼10 K) gas-phase conditions. The conformations of the M+(DB21C7) and M+(DB24C8) complexes were determined by comparing the UVPD spectra with the calculated electronic transitions of the local-minimum forms. The interactions between the electronic excited states of the two benzene chromophores in the M+(DB21C7) and M+(DB24C8) complexes were examined and compared with those of previously studied complexes (dibenzo-15-crown-5 (DB15C5) and dibenzo-18-crown-6 (DB18C6)). The S1-S0 and S2-S0 electronic excitations of the M+(DB21C7) complexes were almost localized in one of the benzene rings. In contrast, the closed conformers of the M+(DB24C8) (M = K, Rb, and Cs) complexes were delocalized over the two chromophores for electronic excitations, exhibiting strong electronic interactions between the benzene rings. For the M+(DB24C8) complexes (M = K, Rb, and Cs), the short distance between the benzene rings (∼3.9 Å) led to a strong interaction between the benzene chromophores. We conclude that this strong interaction in the M+(DB24C8) complexes correlates strongly with the broad absorption in the UVPD spectra, suggesting the presence of an intramolecular excimer for the K+(DB24C8), Rb+(DB24C8), and Cs+(DB24C8) complexes.

Cryogenic Ion Spectroscopy of Protonated and Sodiated Methyladenine Derivatives.

Ultraviolet photodissociation (UVPD) spectra of protonated 9-methyladenine (H+9MA), protonated 7-methyl adenine (H+7MA), protonated 3-methyladenine (H+3MA), and sodiated 7-methyladenine (Na+7MA) near the origin bands of the S0-S1 transition were obtained using cryogenic ion spectroscopy. The UV-UV hole burning, infrared (IR) ion-dip, and IR-UV double resonance spectra showed that all the ions were present as single isomers in a cryogenic ion trap. The UVPD spectrum of H+9MA exhibited only a broad absorption band, whereas the spectra of H+7MA, H+3MA, and Na+7MA displayed moderately or well-resolved vibronic bands. Potential energy profiles were computed to understand the reason for the different bandwidths of the vibronic bands in the spectra. The broadening of the bands was correlated with the slopes between the Franck-Condon point and the conical intersection between the S1 and S0 states in the potential energy profiles, thus reflecting the deactivation rates in the S1 state.

Impact of Internal Fragments on Top-Down Analysis of Intact Proteins by 193 nm UVPD

193 nm ultraviolet photodissociation (UVPD) allows high sequence coverage to be obtained for intact proteins using terminal fragments alone. However, internal fragments, those that contain neither N- nor C- terminus, are typically ignored, neglecting their potential to bolster characterization of intact proteins. Here, we explore internal fragments generated by 193 nm UVPD for proteins ranging in size from 17-47 kDa and using the ClipsMS algorithm to facilitate searches for internal fragments. Internal fragments were only retained if identified in multiple replicates in order to reduce spurious assignments and to explore the reproducibility of internal fragments generated by UVPD. Inclusion of internal fragment improved sequence coverage by an average of 18% and 32% for UVPD and HCD, respectively, across all proteins and charge states studied. However, only an average of 18% of UVPD internal fragments were identified in two out of three replicates relative to the average number identified across all replicates for all proteins studied. Conversely, for HCD, an average of 63% of internal fragments were retained across replicates. These trends reflect an increased risk of false-positive identifications and a need for caution when considering internal fragments for UVPD. Additionally, proton-transfer charge reduction (PTCR) reactions were performed following UVPD or HCD to assess the impact on internal fragment identifications, allowing up to 20% more fragment ions to be retained across multiple replicates. At this time, it is difficult to recommend the inclusion of the internal fragment when searching UVPD spectra without further work to develop strategies for reducing the possibilities of false-positive identifications. All mass spectra are available in the public repository jPOST with the accession number JPST001885.

Temperature dependence of structure investigated by ultraviolet photodissociation spectroscopy of protonated tryptophan dimer

Temperature dependence of electronic and hydrogen-bonded structures was investigated by ultraviolet (UV) photodissociation spectroscopy of protonated tryptophan dimer in the gas phase at 8–120 K in the wavelength range of the S1–S0 transition. The temperature-dependent UV photodissociation spectra of the gas-phase hydrogen-bonded cluster were measured using a tandem mass spectrometer equipped with an electrospray ionization source and a temperature-controlled ion trap. The relative intensity of the band at 289 nm decreased exponentially with increasing temperature, compared to that at 286 nm. The entropic effect caused the most stable compact structure, which was formed from strong cation–π interactions, to undergo conformational changes to flexible extended structures, which predominated above 70 K.

UVPD Spectroscopy of Differential Mobility-Selected Prototropic Isomers of Rivaroxaban.

Two ion populations of protonated Rivaroxaban, [C19H18ClN3O5S + H]+, are separated under pure N2 conditions using differential mobility spectrometry prior to characterization in a hybrid triple quadrupole linear ion trap mass spectrometer. These populations are attributed to bare protonated Rivaroxaban and to a proton-bound Rivaroxaban-ammonia complex, which dissociates prior to mass-selecting the parent ion. Ultraviolet photodissociation (UVPD) and collision-induced dissociation (CID) studies indicate that both protonated Rivaroxaban ion populations are comprised of the computed global minimum prototropic isomer. Two ion populations are also observed when the collision environment is modified with 1.5% (v/v) acetonitrile. In this case, the protonated Rivaroxaban ion populations are produced by the dissociation of the ammonium complex and by the dissociation of a proton-bound Rivaroxaban-acetonitrile complex prior to mass selection. Again, both populations exhibit a similar CID behavior; however, UVPD spectra indicate that the two ion populations are associated with different prototropic isomers. The experimentally acquired spectra are compared with computed spectra and are assigned to two prototropic isomers that exhibit proton sharing between distal oxygen centers.

Gas-Phase UV Spectroscopy of Chemical Intermediates Produced in Solution: Oxidation Reactions of Phenylhydrazines by DDQ.

In this study, we demonstrated cold gas-phase spectroscopy of chemical intermediates produced in solution. Herein, we combined an electrospray ion source with a T-shaped solution mixer for introducing chemical intermediates in solution into the gas phase. Specifically, the oxidation reaction of 2-(4-nitrophenyl)hydrazinecarboxaldehyde (NHCA) by 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was initiated by mixing the methanol solutions of NHCA and DDQ in the T-shaped mixer, and the chemical species were injected into the vacuum apparatus for ultraviolet photodissociation (UVPD) spectroscopy. A cationic intermediate was strongly observed at m/z 150 in the mass spectrum, and the UVPD spectrum was observed under cold (∼10 K) gas-phase conditions. The UVPD spectrum showed a strong, broad absorption at ∼38,000 cm-1, accompanied by a relatively weak component at ∼34,000 cm-1. These spectral patterns can be ascribed to a diazonium cation intermediate, whose existence has been predicted in a previous study. This report indicates that cold gas-phase UV spectroscopy can be a useful method for identifying the structure of chemical intermediates produced in solution.

Versatile Double-Beam Confocal Laser System Combined with a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for Photodissociation Mass Spectrometry and Spectroscopy.

Both infrared multiphoton dissociation (IRMPD) and ultraviolet photodissociation (UVPD) play important roles in tandem mass spectrometry and the action spectroscopy of organic and biological molecules. A flexible combination of the two methods may provide researchers with more versatile and powerful ion activation/dissociation choices for structural characterization and spectroscopic studies. Here, we report the integration of two tunable lasers with a Fourier transform ion cyclotron resonance mass spectrometer in a confocal mode, which offers multiple capabilities for photon activation/dissociation experiments. The two overlapped beams can be introduced into the cell individually, sequentially, or simultaneously, providing highly flexible and diverse activation schemes. The setup can also measure the UVPD or IRMPD action spectra of fragment ions generated by previous photon dissociation processes. In addition, the multistage tandem-in-time mass spectrometry performance up to MS4, including three different activation methods in a single cell, has also been demonstrated.

Phenyl argentate aggregates [AgnPhn+1]- (n = 2-8): Models for the self-assembly of atom-precise polynuclear organometallics.

Electrospray ionization of phenyl argentates formed by transmetalation reactions between phenyl lithium and silver cyanide provides access to the argentate aggregates, [AgnPhn+1]-, which were individually mass-selected for n = 2-8 in order to generate their gas-phase Ultraviolet Photodissociation (UVPD) "action" spectra over the range 304-399nm. A strong bathochromic shift in optical spectra was observed with increasing size/n. Theoretical calculations allowed the assignment of the experimental UVPD spectra to specific isomer(s) and provided crucial insights into the transition from the 2D to 3D structure of the metallic component with the increasing size of the complex. The [AgnPhn+1]- aggregates contain neither pronounced metallic cluster properties nor ligated metallic cluster features and are thus not superatom complexes. They therefore represent novel organometallic characteristics built from Ag2Ph subunits.

Quantification of monosaccharide enantiomers using optical properties of hydrogen-bonded tryptophan

Chiral recognition between amino acids and monosaccharides in the gas phase was investigated as a model for chemical evolution in interstellar molecular clouds. Ultraviolet (UV) photodissociation spectra and product ion spectra of cold gas-phase hydrogen-bonded clusters of protonated tryptophan (Trp) and a pentose, including ribose and arabinose, were obtained using a tandem mass spectrometer equipped with an electrospray ionization source and a temperature-controlled ion trap. The relative intensity of the signal arising from the S1–S0 transition of protonated Trp observed at approximately 285 nm in the UV photodissociation spectrum of homochiral H+(d-Trp)(d-ribose) was significantly higher than that of heterochiral H+(l-Trp)(d-ribose), corresponding to the ππ* state of the Trp indole ring. Optical properties of Trp in the clusters induced by 285-nm photoexcitation were applied to the identification and quantification of pentose enantiomers in solution. Pentose enantiomeric excess in solution was determined from relative abundances observed in a single product ion spectrum of 285-nm photoexcited hydrogen-bonded clusters of H+(l-Trp) and pentose. A mixture of two pentoses could also be quantified by this method. The geometric and electronic structures of Trp enable recognition of biological molecules through hydrogen bonding.

Structure and photochemistry of a potential precursor of circumstellar dust: The optical spectrum of Si4C2+

Mixed silicon carbide clusters are important components of circumstellar shells and their optical properties are fundamental for modelling the chemistry involved in the evolution of dust particles. Herein, we report the ultraviolet photodissociation (UVPD) spectrum of mass-selected Si4C2+ cations obtained in the 208–330 nm range (3.8–6.0 eV) in a quadrupole/time-of-flight tandem mass spectrometer coupled to a laser desorption source operating with a SiC rod and a broadly tuneable optical parametric oscillator laser. The UVPD spectrum is observed in the two lowest-energy fragment channels, corresponding to dominant loss of atomic Si at low energy and the rather stable Si2C molecule at high energy. The UVPD spectrum is analyzed by quantum chemical calculations at two levels of density functional theory (CAM-B3LYP, M11) to determine the structures, energies, electronic spectra, and fragmentation energies of the lowest-energy isomers. To locate these isomers on the multidimensional potential energy surface, basin hopping is employed as global optimization approach. The UVPD spectrum is consistent with the optical absorption spectrum computed for the two lowest-energy isomers, one of which is reported for the first time.

Conformation of K+(Crown Ether) Complexes Revealed by Ion Mobility-Mass Spectrometry and Ultraviolet Spectroscopy.

The conformation and electronic structure of dibenzo-24-crown-8 (DB24C8) complexes with K+ ion were examined by ion mobility-mass spectrometry (IM-MS), ultraviolet (UV) photodissociation (UVPD) spectroscopy in the gas phase, and fluorescence spectroscopy in solution. Three structural isomers of DB24C8 (SymDB24C8, Asym1DB24C8, and Asym2DB24C8) in which the relative positions of the two benzene rings were different from each other were investigated. The IM-MS results at 86 K revealed a clear separation of two sets of conformers for the K+(SymDB24C8) and K+(Asym1DB24C8) complexes whereas the K+(Asym2DB24C8) complex revealed only one set. The two sets of conformers were attributed to the open and closed forms in which the benzene-benzene distances in the complexes were long (>6 Å) and short (<6 Å), respectively. IM-MS at 300 K could not separate the two conformer sets of the K+(SymDB24C8) complex because the interconversion between the open and closed conformations occurred at 300 K and not at 86 K. The crown cavity of DB24C8 was wrapped around the K+ ion in the complex, although the IM-MS results availed direct evidence of rapid cavity deformation and the reconstruction of stable conformers at 300 K. The UVPD spectra of the K+(SymDB24C8) and K+(Asym1DB24C8) complexes at ∼10 K displayed broad features that were accompanied by a few sharp vibronic bands, which were attributable to the coexistence of multiple conformers. The fluorescence spectra obtained in a methanol solution suggested that the intramolecular excimer was formed only in K+(SymDB24C8) among the three complexes because only SymDB24C8 could possibly assume a parallel configuration between the two benzene rings upon K+ encapsulation. The encapsulation methods for K+ ion (the "wraparound" arrangement) are similar in the three structural isomers of DB24C8, although the difference in the relative positions of the two benzene rings affected the overall cross-section. This study demonstrated that temperature-controlled IM-MS coupled with the introduction of appropriate bulky groups, such as aromatic rings to host molecules, could reveal the dynamic aspects of encapsulation in host-guest systems.

Identification and quantification of leucine and isoleucine residues in peptides using photoexcited tryptophan.

The molecular recognition ability of tryptophan (Trp) for isomeric amino acids, such as leucine (Leu) and isoleucine (Ile), and isomeric amino acid-containing dipeptides, such as Leu-Gly, Ile-Gly, Gly-Leu, and Gly-Ile (where Gly denotes glycine), was investigated using a tandem mass spectrometer equipped with an electrospray ionization source and cold ion trap. The ultraviolet photodissociation spectra of the cold gas-phase clusters of Leu and Ile with Na+Trp in the wavelength range of 265-290nm revealed that the relative intensities of Leu and Ile were only different in the wavelength range of 265-273nm; however, no differences in the relative intensities were observed when the wavelength exceeded 274nm. The molecular recognition ability of photoexcited Trp was used for the identification and quantification of Leu and Ile in dipeptides in solution. The mole fractions of Leu and Ile in dipeptides could be determined from the abundances observed in a single product ion spectrum of the cold gas-phase clusters of dipeptides with Na+Trp.

Wavelength-Dependent Ultraviolet Photodissociation of Protonated Tryptamine.

Ultraviolet photodissociation (UVPD) experiments of protonated tryptamine ([Tryp+H]+) have been implemented by a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer combined with a wavelength-tunable optical parametric oscillator (OPO) laser. UVPD mass spectra under different laser wavelengths have been obtained, in which the dependence of the yield of fragment ions on the laser wavelength was observed. The UVPD spectrum of [Tryp+H]+ has been obtained in the range of 210-310 nm. Besides the previously reported two competitive channels of H loss and NH3 loss, two important channels of losing CH2NH and CH2NH2 units were observed and further studied by UV-UV tandem mass spectrometry and theoretical calculations. Interestingly, results show that the pair of competitive channels of CH2NH loss and CH2NH2 loss are both from the McLafferty-type rearrangement caused by ππ* electronic excited states. After the excitation, the two different dissociation pathways produce two different ion-neutral complexes, respectively. The wavelength-dependent dissociation and the existing competitive channels shown in this study reflect the diversity of UVPD processes of such organic molecules.

Ultraviolet Photodissociation of Tryptic Peptide Backbones at 213 nm.

We analyzed the backbone fragmentation behavior of tryptic peptides of a four-protein mixture and of E. coli lysate subjected to ultraviolet photodissociation (UVPD) at 213 nm on a commercially available UVPD-equipped tribrid mass spectrometer. We obtained 15 178 unique high-confidence peptide UVPD spectrum matches by recording a reference beam-type collision-induced dissociation (HCD) spectrum of each precursor, ensuring that our investigation includes a broad selection of peptides, including those that fragmented poorly by UVPD. Type a, b, and y ions were most prominent in UVPD spectra, and median sequence coverage ranged from 5.8% (at 5 ms laser excitation time) to 45.0% (at 100 ms). Overall, the sequence fragment intensity remained relatively low (median: 0.4% (5 ms) to 16.8% (100 ms) of total intensity), and the remaining precursor intensity, high. The sequence coverage and sequence fragment intensity ratio correlated with the precursor charge density, suggesting that UVPD at 213 nm may suffer from newly formed fragments sticking together due to noncovalent interactions. The UVPD fragmentation efficiency therefore might benefit from supplemental activation, as was shown for ETD. Aromatic amino acids, most prominently tryptophan, facilitated UVPD. This points to aromatic tags as possible enhancers of UVPD. Data are available via ProteomeXchange with identifier PXD018176 and on spectrumviewer.org/db/UVPD-213nm-trypPep.

Structural Evaluation of Protein/Metal Complexes via Native Electrospray Ultraviolet Photodissociation Mass Spectrometry.

Ultraviolet photodissociation (UVPD) has emerged as a promising tool to characterize proteins with regard to not only their primary sequences and post-translational modifications, but also their tertiary structures. In this study, three metal-binding proteins, Staphylococcal nuclease, azurin, and calmodulin, are used to demonstrate the use of UVPD to elucidate metal-binding regions via comparisons between the fragmentation patterns of apo (metal-free) and holo (metal-bound) proteins. The binding of staphylococcal nuclease to calcium was evaluated, in addition to a series of lanthanide(III) ions which are expected to bind in a similar manner as calcium. On the basis of comparative analysis of the UVPD spectra, the binding region for calcium and the lanthanide ions was determined to extend from residues 40-50, aligning with the known crystal structure. Similar analysis was performed for both azurin (interrogating copper and silver binding) and calmodulin (four calcium binding sites). This work demonstrates the utility of UVPD methods for determining and analyzing the metal binding sites of a variety of classes of proteins.

Induced Fit of Crown Cavity to Ammonium Ion Guests and Photoinduced Intracavity Reactions: Cold Gas-Phase Spectroscopy of Dibenzo-18-Crown-6 Complexes with NH4+, CH3NH3+, and CH3CH2NH3.

Ultraviolet photodissociation (UVPD) spectra of dibenzo-18-crown-6 (DB18C6) complexes with NH4+, CH3NH3+ (MeNH3+), and CH3CH2NH3+ (EtNH3+) [NH4+(DB18C6), MeNH3+(DB18C6), and EtNH3+(DB18C6), respectively] were observed under cold gas-phase conditions. We also measured the infrared (IR)-UV double-resonance spectra of these complexes in the NH stretching region to examine the encapsulation structure. The UVPD and IR-UV spectra were analyzed using quantum chemical calculations. All the ammonium complexes show sharp 0-0 bands at positions close to that of the K+(DB18C6) complex; the conformation of the DB18C6 component in the ammonium complexes is similar to that in K+(DB18C6). In addition, the ammonium complexes each have another type of isomer that the K+(DB18C6) complex does not show in the gas phase. In these isomers, the conformation of the DB18C6 cavity changes, and the strength of the NH···O hydrogen bond increases. During the UVPD, the NH4+(DB18C6) complex provides various photofragment species, such as the C8H9O2+ ion, resulting from cleavage of the DB18C6 component, whereas the dominant fragment ion for the MeNH3+(DB18C6) and EtNH3+(DB18C6) complexes is the ammonium ion itself. The UVPD investigation of deuterated systems suggests that after UV excitation of the NH4+(DB18C6) complex, the dissociation process is initiated by proton transfer from NH4+ to DB18C6, followed by the migration of hydrogen atoms in the crown cavity and the cleavage of the ether ring.