Search

The 2'-substituents distinguish DNA from RNA nucleosides. 2'-O-methylation occurs naturally in RNA and plays important roles in biological processes. Such 2'-modifications may alter the hydrogen-bonding interactions of the nucleoside and thus may affect the conformations of the nucleoside in an RNA chain. Structures of the protonated 2'-O-methylated pyrimidine nucleosides were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy, assisted by electronic structure calculations. The glycosidic bond stabilities of the protonated 2'-O-methylated pyrimidine nucleosides, [Nuom+H]+, were also examined and compared to their DNA and RNA nucleoside analogues via energy-resolved collision-induced dissociation (ER-CID). The preferred sites of protonation of the 2'-O-methylated pyrimidine nucleosides parallel their canonical DNA and RNA nucleoside analogues, [dNuo+H]+ and [Nuo+H]+, yet their nucleobase orientation and sugar puckering differ. The glycosidic bond stabilities of the protonated pyrimidine nucleosides follow the order: [dNuo+H]+ < [Nuo+H]+ < [Nuom+H]+. The slightly altered structures help explain the stabilization induced by 2'-O-methylation of the pyrimidine nucleosides.

The gas-phase structures of protonated unsymmetrical 1,1-dimethylhydrazine (UDMH) and the proton-bound dimers of UDMH and hydrazine are examined by infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light generated by a free electron laser and an optical parametric oscillator laser system. To identify the structures present in the experimental studies, the measured IRMPD spectra are compared to spectra calculated at the B3LYP-GD3BJ/6-311+G(d,p) level of theory. These comparisons show that protonated UDMH binds the proton at the methylated nitrogen atom (α) with two low-lying α conformers probably being populated. For (UDMH)2H+, the proton is shared between the methylated nitrogen atoms with several low-lying α conformers likely to be populated. Higher-lying conformers of (UDMH)2H+ in which the proton is shared between α and β (unmethylated) nitrogen atoms cannot be ruled out on the basis of the IRPMD spectrum. For (N2H4)2H+, there are four low-lying conformers that all reproduce the IRMPD spectrum reasonably well. As hydrazine and UDMH see usage as fuels for rocket engines, such spectra are potentially useful as a means of remotely monitoring rocket launches, especially in cases of unsuccessful launches where environmental hazards need to be assessed.

The first absolute experimental bond dissociation energies (BDEs) for the main heterolytic bond cleavages of four benzylpyridinium “thermometer” ions are measured using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. In this experiment, substituted benzylpyridinium ions are introduced into the apparatus using an electrospray ionization source, thermalized, and collided with Xe at varied kinetic energies to determine absolute cross-sections for these reactions. Various effects are accounted for, including kinetic shifts, multiple collisions, and internal and kinetic energy distributions. These experimentally measured 0 K BDEs are compared with computationally predicted values at the B3LYP-GD3BJ, M06-GD3, and MP2(full) levels of theory with a 6-311+G(2d,2p) basis set using vibrational frequencies and geometries determined at the B3LYP/6-311+G(d,p) level. Additional dissociation pathways are observed for nitrobenzylpyridinium experimentally and investigated using these same levels of theory. Experimental BDEs are also compared against values in the literature at the AM1, HF, B3LYP, B3P86, and CCSD(T) levels of theory. Of the calculated values obtained in this work, the MP2(full) level of theory with counterpoise corrections best reproduces the experimental results, as do the similar literature CCSD(T) values. Lastly, the survival yield method is used to determine the characteristic temperature (Tchar) of the electrospray source prior to the thermalization region and to confirm efficient thermalization.

Threshold collision-induced dissociation (TCID) using a guided ion beam tandem mass spectrometer is performed on (N2H4)nH+ where n = 2–4 and on the proton-bound unsymmetrical 1,1-dimethylhydrazine (UDMH) dimer complex. The primary dissociation pathway for all reactants consists of loss of a single hydrazine (or UDMH) molecule followed by the sequential loss of additional hydrazine molecules at higher collision energies for n = 3 and 4. The data were analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies (BDEs). These are also converted to values at room temperature by using a rigid rotor/harmonic oscillator approximation and theoretical molecular constants. Experimental BDEs are compared to theoretical BDEs determined at the B3LYP, M06, mPW1PW91, PBE0, MP2(full), and CCSD(T) levels of theory with and without empirical dispersion with a 6-311+G(2d,2p) basis set. The structures of all...

Complexes of 18-crown-6 ether (18C6) with four protonated amino acids (AAs) are examined using infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light generated by the infrared free electron laser at the Centre Laser Infrarouge d'Orsay (CLIO). The AAs examined in this work include glycine (Gly) and the three basic AAs: histidine (His), lysine (Lys), and arginine (Arg). To identify the (AA)H+(18C6) conformations present in the experimental studies, the measured IRMPD spectra are compared to spectra calculated at the B3LYP/6-311+G(d,p) level of theory. Relative energies of various conformers and isomers are provided by single point energy calculations carried out at the B3LYP, B3P86, M06, and MP2(full) levels using the 6-311+G(2p,2d) basis set. The comparisons between the IRMPD and theoretical IR spectra indicate that 18C6 binds to Gly and His via the protonated backbone amino group, whereas protonated Lys prefers binding via the protonated side-chain amino group. Results for Arg are less definitive with strong evidence for binding to the protonated guanidino side chain (the calculated ground conformer at most levels of theory), but contributions from backbone binding to a zwitterionic structure are likely.

The gas-phase structures of zinc and cadmium dications bound to serine (Ser) are investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using the free electron laser FELIX, in combination with ab initio calculations. To identify the structures of the experimentally observed species, [Zn(Ser-H)CH3CN](+) and CdCl(+)(Ser), the measured action spectra are compared to linear absorption spectra calculated at the B3LYP/6-311+G(d,p) level for Zn(2+) containing complexes and B3LYP/def2-TZVP levels for Cd(2+) containing complexes. Good agreement between the observed IRMPD spectra and the predicted spectra allows identification of the isomers present. The intact amino acid interacting with cadmium chloride adopts a tridentate chelation involving the amino acid backbone amine and carbonyl groups as well as the hydroxyl group of the side-chain, [N,CO,OH]. The presence of two low-energy conformers is observed for the deprotonated serine-zinc complex, with the same tridentate coordination as for the cadmium complex but proton loss occurs at both the hydroxyl side-chain, [N,CO,O(-)], and the carboxylic acid of the amino acid backbone, [N,CO(-),OH]. These results are profitably compared with the analogous results previously obtained for comparable complexes with cysteine.

International audience; The chemical difference between DNA and RNA nucleosides is their 2′-hydrogen versus 2′-hydroxyl substituents. Modification of the ribosyl moiety at the 2′-position and 2′-O-methylation in particular, is common among natural post-transcriptional modifications of RNA. 2′-Modification may alter the electronic properties and hydrogen-bonding characteristics of the nucleoside and thus may lead to enhanced stabilization or malfunction. The structures and relative glycosidic bond stabilities of the protonated forms of the 2′-O-methylated purine nucleosides, 2′-O-methyladenosine (Adom) and 2′-O-methylguanosine (Guom), were examined using two complementary tandem mass spectrometry approaches, infrared multiple photon dissociation action spectroscopy and energy-resolved collision-induced dissociation. Theoretical calculations were also performed to predict the structures and relative stabilities of stable low-energy conformations of the protonated forms of the 2′-O-methylated purine nucleosides and their infrared spectra in the gas phase. Low-energy conformations highly parallel to those found for the protonated forms of the canonical DNA and RNA purine nucleosides are also found for the protonated 2′-O-methylated purine nucleosides. Importantly, the preferred site of protonation, nucleobase orientation, and sugar puckering are preserved among the DNA, RNA, and 2′-O-methylated variants of the protonated purine nucleosides. The 2′-substituent does however influence hydrogen-bond stabilization as the 2′-O-methyl and 2′-hydroxyl substituents enable a hydrogen-bonding interaction between the 2′- and 3′-substituents, whereas a 2′-hydrogen atom does not. Further, 2′-O-methylation reduces the number of stable low-energy hydrogen-bonded conformations possible and importantly inverts the preferred polarity of this interaction versus that of the RNA analogues. Trends in the CID50% values extracted from survival yield analyses of the 2′-O-methylated and canonical DNA and RNA forms of the protonated purine nucleosides are employed to elucidate their relative glycosidic bond stabilities. The glycosidic bond stability of Adom is found to exceed that of its DNA and RNA analogues. The glycosidic bond stability of Guom is also found to exceed that of its DNA analogue; however, this modification weakens this bond relative to its RNA counterpart. The glycosidic bond stability of the protonated purine nucleosides appears to be correlated with the hydrogen-bond stabilization of the sugar moiety.

Complexes of aspartic acid (Asp) cationized with Zn

Complexes of aspartic acid (Asp) cationized with Zn2+: Zn(Asp-H)+, Zn(Asp-H)+(ACN) where ACN = acetonitrile, and Zn(Asp-H)+(Asp); as well as with Cd2+, CdCl+(Asp), were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free electron laser. A series of low-energy conformers for each complex was found using quantum chemical calculations to identify the structures formed experimentally. The main binding motif observed for the heavy-metal complex, CdCl+(Asp)[N,CO,COs], is a charge-solvated, tridentate structure, where the metal center binds to the backbone amino group and carbonyl oxygens of the backbone and side-chain carboxylic acids. Likewise, the deprotonated Zn(Asp-H)+(ACN) and Zn(Asp-H)+(Asp) complexes show comparable [N,CO–,COs](ACN) and [N,CO–,COs][N,CO,COs] coordinations, respectively. Interestingly, there was only minor spectral evidence for the analogous Zn(Asp-H)+[N,CO–,COs] binding motif, even though this species is predicted to be the lowest-energy conformer. Instead, rearrangement and partial dissociation of the amino acid are observed, as spectral features most consistent with the experimental spectrum are exhibited by a four-coordinate Zn(Asp-NH4)+[CO2–,COs](NH3) complex. Analysis of the mechanistic pathway leading from the predicted lowest-energy conformer to the isobaric deaminated complex is explored theoretically. Further, comparison of the current work to that of Zn2+ and Cd2+ complexes of asparagine (Asn) allows additional conclusions regarding populated conformers and effects of carboxamide versus carboxylic acid binding to be drawn.

Structural characterization of gas-phase ions of cysteine (Cys) and cysteine methyl ester (CysOMe) complexed to zinc and cadmium is investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using a free electron laser in combination with density functional theory calculations. IRMPD spectra are measured for [Zn(Cys-H)](+), [Cd(Cys-H)](+), [Zn(CysOMe-H)](+), [Cd(CysOMe-H)](+) and CdCl(+)(CysOMe) and are accompanied by quantum mechanical calculations of the predicted linear absorption spectra at the B3LYP/6-311+G(d,p) (Zn(2+) complexes) and B3LYP/def2TZVP levels (Cd(2+) complexes). On the basis of these experiments and calculations, the conformation that best reproduces the IRMPD spectra for the complexes of the deprotonated amino acids, [M(Cys-H)](+) and [M(CysOMe-H)](+), is a charge-solvated (CS) tridentate structure where the metal dication binds to the amine and carbonyl groups of the amino acid backbone and the deprotonated sulfur atom of the side chain, [N,CO,S(-)]. The intact amino acid complex, CdCl(+)(CysOMe) binds in the equivalent motif [N,CO,S]. These binding motifs are in agreement with the predicted ground structures of these complexes at the B3LYP, B3LYP-GD3BJ (with empirical dispersion corrections), B3P86, and MP2(full) levels.

Threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer is performed on (N2H4)H+(H2O)n, where n = 1 and 2, and on the protonated unsymmetrical 1,1-dimethylhydrazine one-water complex. The primary dissociation pathway for all clusters is a loss of a single water molecule, which for n = 2 is followed by the sequential loss of an additional water molecule at higher collision energies. The data are analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies (BDEs). These are also converted using a rigid rotor/harmonic oscillator approximation to yield thermodynamic values at room temperature. Experimental BDEs compare favorably to theoretical BDEs determined at the B3LYP, M06, mPW1PW91, PBE0, MP2(full), and CCSD(T) levels of theory with a 6-311+G(2d,2p) basis set both with and without empirical dispersion. These calculations also allow visualization of the s...

Correction for ‘Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy’ by Rebecca A. Coates et al., Phys. Chem. Chem. Phys., 2015, 17, 25799–25808.

Correction for 'Zn

Complexes of glutamic acid (Glu) cationized with Zn2+ and Cd2+ were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free electron laser. Complexes of deprotonated Glu with Zn2+, [Zn(Glu-H)ACN](+) (where ACN = acetonitrile, CH3CN), and intact Glu with CdCl+, CdCl+(Glu) were formed. Notably, photodissociation induces Glu fragmentation rather than ACN loss in the Zn2+ complex. In order to identify the structures formed experimentally, the experimentally obtained spectra were compared to those calculated from optimized structures at the B3LYP/6-311+G(d,p) level for [Zn(Glu-H)ACN](+) and B3LYP/def2-TZVP level with an SDD effective core potential on cadmium for the CdCl+(Glu) system. The main binding motif observed for the heavy metal complex is a charge solvated, tridentate [N, COs, CO] structure where the metal binds to the backbone amino group and carbonyl oxygens of the side-chain and backbone carboxylic acid groups. The Zn2+ system similarly prefers a [N, CO-, COs] binding motif, where binding is observed at one oxygen of the backbone carboxylate site along with the backbone amino and side-chain carbonyl groups. In both cases, the theoretically determined lowest-energy conformers explain the experimental [Zn(Glu-H)ACN](+) and CdCl+(Glu) spectra well.

The energy dependences of size-selected Fen(+) cluster ions (n = 1-17) reacting with CO at low energies are studied using a guided ion beam tandem mass spectrometer equipped with a laser vaporization source. Below about 1 eV, all clusters with n ≥ 4 form the FenCO(+) association complex. The probability of this reaction increases with cluster size until the absolute cross sections equal the collision limit for n10, with those for n = 12 and 14 exceeding the collision limit. As the cluster size increases, a second pathway becomes prominent at higher energies. The kinetic energy dependence and absolute magnitudes of these cross sections are analyzed to extract cluster-CO binding energies, which are found to progressively decrease with increasing cluster size, consistent with a simple Coulomb model. For the largest clusters, these binding energies approach that of an extended surface at shallow hollow sites, whereas the higher energy feature correlates with binding energies for dissociatively chemisorbed C and O on an iron surface.

Correction for ‘Zn2+ and Cd2+ cationized serine complexes: infrared multiple photon dissociation spectroscopy and density functional theory investigations’ by Rebecca A. Coates et al., Phys. Chem. Chem. Phys., 2016, 18, 22434–22445.

Threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer was performed on protonated hydrazine and its perdeuterated variant. The dominant dissociation pathways observed were endothermic homolytic and heterolytic cleavages of the N–N bond. The data were analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies. Comparison with literature thermochemistry demonstrates that both channels behave non-adiabatically. Heterolytic bond cleavage yields NH2+ + NH3 products, but the NH2+ fragment is in the spin-restricted excited 1A1 state and not in the spin-forbidden ground 3B1 state, whereas homolytic bond cleavage leads to dissociation to the NH3+ + NH2 product asymptote with NH2 in its excited 2A1 state rather than the energetically favored 2B1 state. The rationale for the non-adiabatic behavior observed in the homolytic bond cleavage is revealed by detailed t...