The demand for nanoscale materials of ultra-high purity and narrow size distribution is addressed. Clusters of Au, C60, H2O, and serine are produced inside helium nanodroplets using a combination of ionization, mass filtering, collisions with atomic or molecular vapor, and electrostatic extraction, in a specific and novel sequence. The helium droplets are produced in an expansion of cold helium gas through a nozzle into vacuum. The droplets are ionized by electron bombardment and subjected to a mass filter. The ionic and mass-selected helium droplets are then guided through a vacuum chamber filled with atomic or molecular vapor where they collide and “pick up” the vapor. The dopants then agglomerate inside the helium droplets around charge centers to singly charged clusters. Evaporation of the helium droplets is induced by collisions in a helium-filled radio frequency (RF)-hexapole, which liberates the cluster ions from the host droplets. The clusters are analyzed with a time-of-flight mass spectrometer. It is demonstrated that using this sequence, the size distribution of the dopant cluster ions is distinctly narrower compared to ionization after pickup. Likewise, the ion cluster beam is more intense. The mass spectra show, as well, that ion clusters of the dopants can be produced with only few helium atoms attached, which will be important for messenger spectroscopy. All these findings are important for the scientific research of clusters and nanoscale materials in general.
28 October 2018 in The Journal of Chemical Physics
5-trifluoromethanesulfonyl-uracil (OTfU), a recently proposed radiosensitizer, is decomposed in the gas-phase by attachment of low-energy electrons. OTfU is a derivative of uracil with a triflate (OTf) group at the C5-position, which substantially increases its ability to undergo effective electron-induced dissociation. We report a rich assortment of fragments formed upon dissociative electron attachment (DEA), mostly by simple bond cleavages (e.g., dehydrogenation or formation of OTf−). The most favorable DEA channel corresponds to the formation of the triflate anion alongside with the reactive uracil-5-yl radical through the cleavage of the O–C5 bond, particularly at about 0 eV. Unlike for halouracils, the parent anion was not detected in our experiments. The experimental findings are accounted by a comprehensive theoretical study carried out at the M06-2X/aug-cc-pVTZ level. The latter comprises the thermodynamic thresholds for the formation of the observed anions calculated under the experimental conditions (383.15 K and 3 × 10−11 atm). The energy-resolved ion yield of the dehydrogenated parent anion, (OTfU–H)−, is discussed in terms of vibrational Feshbach resonances arising from the coupling between the dipole bound state and vibrational levels of the transient negative ion. We also report the mass spectrum of the cations obtained through ionization of OTfU by electrons with a kinetic energy of 70 eV. The current study endorses OTfU as a potential radiosensitizer agent with possible applications in radio-chemotherapy.
16 June 2020 in Angewandte Chemie International Edition
Tirapazamine (TPZ) has been tested in clinical trials on radio‐chemotherapy due to its potential highly selective toxicity towards hypoxic tumor cells. It was suggested that either the hydroxyl radical or benzotriazinyl radical may form as bioactive radical after the initial reduction of TPZ in solution. In the present work, we studied low‐energy electron attachment to TPZ in the gas phase and investigated the decomposition of the formed TPZ− anion by mass spectrometry. We observed the formation of the (TPZ–OH)− anion accompanied by the dissociation of the hydroxyl radical as by far the most abundant reaction pathway upon attachment of a low‐energy electron. Quantum chemical calculations suggest that NH2 pyramidalization is the key reaction coordinate for the reaction dynamics upon electron attachment. We propose an OH roaming mechanism for other reaction channels observed, in competition with the OH dissociation.
Laboratory studies play a crucial role in understanding the chemical nature of the interstellar medium (ISM), but the disconnect between experimental timescales and the timescales of reactions in space can make a direct comparison between observations, laboratory, and model results difficult. Here we study the survival of reactive fragments of the polycyclic aromatic hydrocarbon (PAH) coronene, where individual C atoms have been knocked out of the molecules in hard collisions with He atoms at stellar wind and supernova shockwave velocities. Ionic fragments are stored in the DESIREE cryogenic ion-beam storage ring where we investigate their decay for up to one second. After 10 ms the initially hot stored ions have cooled enough so that spontaneous dissociation no longer takes place at a measurable rate; a majority of the fragments remain intact and will continue to do so indefinitely in isolation. Our findings show that defective PAHs formed in energetic collisions with heavy particles may survive at thermal equilibrium in the interstellar medium indefinitely, and could play an important role in the chemistry in there, due to their increased reactivity compared to intact or photo-fragmented PAHs.
DNA nanotechnology holds great promise for development of a lab-on-a-DNA origami. We summarize the latest trends based on DNA origami focusing on light-harvesting nanoantennas and platforms for single-molecule optical spectroscopy and/or atomic force microscopy (AFM).
17 May 2021 in Journal of the American Society for Mass Spectrometry