Article
Chemistry, Physical
Walter E. Olmedo, Liliana B. Jimenez, Andres F. Cruz-Ortiz, Philippe Maitre, Gustavo A. Pino, Maximiliano Rossa
Summary: This study presents the first structural characterization of protonated cyameluric acid ([CA + H](+)) in the gas phase, revealing that the available O positions on neutral CA are energetically favored protonation sites. Ab initio computations predict different reduced isomer populations of [CA + H](+) in solution and gas phases, indicating the occurrence of isomer interconversion reactions during their transfer into the gas phase.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Brandon Lu, Yoel P. Ohayon, Karol Woloszyn, Chu-fan Yang, Jesse B. Yoder, Lynn J. Rothschild, Shalom J. Wind, Wayne A. Hendrickson, Chengde Mao, Nadrian C. Seeman, James W. Canary, Ruojie Sha, Simon Vecchioni
Summary: This study explores the application of metal-mediated DNA (mmDNA) in engineering bioinorganic and electronic characteristics. Through crystallography, it is found that silver(I) has an increased binding occupancy with T-T and U-U base pairs at high pH levels. This property is used to capture the structure of silver(I) and mercury(II) within the same base pair. The study also captures cadmium(II) and mercury(II) in T-T base pairs using the same pattern. These findings provide possibilities for atomistic design frameworks for more complex mmDNA-based nanodevices and nanotechnologies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Giuseppe Mattioli, Lorenzo Avaldi, Paola Bolognesi, John D. Bozek, Mattea C. Castrovilli, Jacopo Chiarinelli, Alicja Domaracka, Suvasthika Indrajith, Sylvain Maclot, Aleksandar R. Milosavljevi, Chiara Nicolafrancesco, Patrick Rousseau
Summary: The properties of mixed water-uracil nanoaggregates were investigated through core electron-photoemission measurements and atomistic simulations, revealing a complex atomistic description of the molecular structure and organization. The unique skeletal features of uracil contribute to the core-shell-like structure of the mixed clusters, distinct from typical solid-state hydration or liquid solvation models.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Liangyi Chen, Zifan Ma, Joseph A. Fournier
Summary: This study presents ultrafast transient vibrational action spectra of cryogenically cooled Re(CO)(3)(CH3CN)(3)(+) ions. Nonlinear spectra were collected in the time domain by monitoring the photodissociation of a weakly bound N-2 messenger tag. In the carbonyl stretch region, frequency-resolved spectra show relatively strong bleaching signals that oscillate at the difference frequency between the two observed vibrational features. This observation suggests the presence of nonlinear pathways resulting from underlying cross-peak signals between the coupled symmetric-asymmetric C & EQUIV;O stretch pair.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yanrong Jiang, Qinqin Yuan, Wenjin Cao, Zhubin Hu, Yan Yang, Cheng Zhong, Tao Yang, Haitao Sun, Xue-Bin Wang, Zhenrong Sun
Summary: This study reveals the important role of hydrogen bonds in water environments and demonstrates that B-H···O DHBs are stronger than conventional B-X···O HBs.
Article
Chemistry, Physical
Benjamin McKinnon, Samuel J. P. Marlton, Jordan Dezalay, Satchin Soorkia, Stephen J. Blanksby, Adam J. Trevitt
Summary: This study investigates the first pi pi* transition for protonated 2-, 3-, and 4-formylpyridine (FPH+) using mass spectrometry coupled with photodissociation action spectroscopy. The findings reveal the photodissociation pathways and product distributions for different ions. While the elimination of CO is thermodynamically preferred, the loss of CH2O also shows kinetic competitiveness. This study is important for understanding the photochemical properties of these ionized compounds.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Christoph Jessen, Andreas J. Kornath
Summary: In this study, the protonation reaction of acetylenedicarboxylic acid and the crystal structures of its salts were investigated in the binary superacidic systems HF/MF5 (M=As, Sb). Both mono- and diprotonated acetylenedicarboxylic acid were obtained depending on the stoichiometric ratio of Lewis acid. The mono- and diprotonated salts exhibited different crystal structures, with the latter being characterized by single-crystal X-ray structure analysis. Quantum chemical calculations were also conducted to support the experimental results.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Spectroscopy
Dietmar Kuck
Summary: This article presents the development of gas-phase chemistry of protonated methylbenzenes and their higher congeners by mass spectrometric methodology, focusing on isomerization and fragmentation mechanisms of different C7H9+ ions and the application of techniques such as infrared spectroscopy. The complex energy hypersurface of toluenium ions and the role of such species in acidic zeolite catalysts are also discussed.
MASS SPECTROMETRY REVIEWS
(2021)
Article
Multidisciplinary Sciences
Rocio Borrego-Varillas, Artur Nenov, Piotr Kabacinski, Irene Conti, Lucia Ganzer, Aurelio Oriana, Vishal Kumar Jaiswal, Ines Delfino, Oliver Weingart, Cristian Manzoni, Ivan Rivalta, Marco Garavelli, Giulio Cerullo
Summary: Researchers have found that 5-methyluridine has a lifespan an order of magnitude longer than uridine due to solvent reorganization needed for bulky methyl group motion. The photophysical mechanism by which nucleosides dissipate energy after UV light irradiation remains a topic of debate.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Oskar Asvany, Stephan Schlemmer
Summary: Rotational action spectroscopy is an experimental method used to record rotational spectra of molecules by action spectroscopy, rather than by detecting absorption of light by the molecules. Mainly applied to molecular ions, this method was initially limited by the low energy content of photons, but today there are various rotational action spectroscopic schemes available.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Samuel J. P. Marlton, Benjamin McKinnon, Phillip Greissel, Oisin J. Shiels, Boris Ucur, Adam J. Trevitt
Summary: This study investigates the role of a protonated N-N chemical group in the excited-state deactivation of protonated indazole compared to its isomer protonated benzimidazole. Protonated indazole exhibits shorter lifetimes attributed to pi sigma* state mediated elongation of the protonated N-N bond, as determined by experimental results, quantum chemical calculations, and potential energy surfaces.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Dongbo Mi, Junqiang Xu, Yunpeng Zhang, Tenggao Zhu, Jiewen Ouyang, Xiaofeng Dong, Konstantin Chingin
Summary: Protonated water-hydrogen clusters [H+(H2O)(n)center dot m(H-2)] can be produced at room temperature through the association of protonated water clusters H+(H2O)(n) with H-2 gas, without any cooling necessary. A proposed mechanism for the formation of the protonated water-hydrogen complexes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Physics, Atomic, Molecular & Chemical
Sven Thorwirth, Oskar Asvany, Michael E. Harding, Pavol Jusko, Michael C. McCarthy, Sandra Bruenken, Stephan Schlemmer
Summary: The infrared action spectra of protonated forms of two fundamental organic nitriles, vinyl cyanide and ethyl cyanide, were observed and analyzed through anharmonic force field calculations and quantum-chemical calculations. The results indicate that the neon atom is attached to the proton bound to the nitrile group in both molecular ions.
JOURNAL OF MOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Multidisciplinary
Graham A. Cooper, Connor J. Clarke, Jan R. R. Verlet
Summary: When high-energy radiation passes through aqueous material, low-energy electrons are produced which cause DNA damage. Electronic states of anionic nucleobases have been suggested as an entrance channel to capture the electron. However, identifying these electronic resonances have been restricted to gas-phase electron-nucleobase studies and offer limited insight into the resonances available within the aqueous environment of DNA. Here, resonance and detachment energies of the micro-hydrated uracil pyrimidine nucleobase anion are determined by two-dimensional photoelectron spectroscopy and are shown to extrapolate linearly with cluster size. This extrapolation allows the corresponding resonance and detachment energies to be determined for uracil in aqueous solution as well as the reorganization energy associated with electron capture. Two shape resonances are clearly identified that can capture low-energy electrons and subsequently form the radical anion by solvent stabilization and internal conversion to the ground electronic state. The resonances and their dynamics probed here are the nucleobase-centered doorway states for low-energy electron capture and damage in DNA.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Analytical
Courtney A. Cruse, John Goodpaster
Summary: Gas chromatography/vacuum UV spectroscopy was used to study the gas phase VUV spectra of various nitrated compounds. The absorption characteristics of the nitro functional group were found to vary depending on the structure of the molecule, with different compounds exhibiting unique absorption patterns in the vacuum UV region. The diversity of the spectra analyzed could be reliably differentiated using PCA and LDA techniques.
ANALYTICA CHIMICA ACTA
(2021)