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Plasmon-driven chemical conversion is gaining burgeoning interest in the field of heterogeneous catalysis. Herein, we study the reactivity of N-methyl-4-sulfanylbenzamide (NMSB) at nanocavities of gold and silver nanoparticle aggregates under plasmonic excitation to gain understanding of the respective reaction mechanism. NMSB is a secondary amide, which is a frequent binding motive found in peptides and a common coupling product of organic molecules and biomolecules. Surface-enhanced Raman scattering (SERS) is used as a two-in-one in-situ spectroscopic tool to initiate the molecular transformation process and simultaneously monitor and analyze the reaction products. Supported by dissociative electron attachment (DEA) studies with the gas phase molecule, a hot electron-mediated conversion of NMSB to p-mercaptobenzamide and p-mercaptobenzonitrile is proposed at the plasmonic nanocavities. The reaction rate showed negligible dependence on the external temperature, ruling out the dominant role of heat in the chemical transformation at the plasmonic interface. This is reflected in the absence of a superlinear relationship between the reaction rate constant and the laser power density, and DEA and SERS studies indicate a hot-electron mediated pathway. We conclude that the overall reaction rate is limited by the availability of energetic hot electrons to the NMSB molecule.
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Radiation cancer therapies use different ionizing radiation qualities that damage DNA molecules in tumor cells by a yet not completely understood plethora of mechanisms and processes. While the direct action of the radiation is significant, the byproducts of the water radiolysis, mainly secondary low-energy electrons (LEEs, <20 eV) and reactive oxygen species (ROS), can also efficiently cause DNA damage, in terms of DNA strand breakage or DNA interstrand cross-linking. As a result, these types of DNA damage evolve into mutations hindering DNA replication, leading to cancer cell death. Concomitant chemo-radiotherapy explores the addition of radiosensitizing therapeutics commonly targeting DNA, such as platinum derivatives and halogenated nucleosides, to enhance the harmful effects of ionizing radiation on the DNA molecule. Further complicating the landscape of DNA damage are secondary structures such as G-quadruplexes occurring in telomeric DNA. These structures protect DNA from radiation damage, rendering them as promising targets for new and more selective cancer radiation treatments, rather than targeting linear DNA. However, despite extensive research, there is no single paradigm approach to understanding the mysterious way in which ionizing radiation causes DNA damage. This is due to the multidisciplinary nature of the field of research, which deals with multiple levels of biological organization, from the molecular building blocks of life toward cells and organisms, as well as with complex multiscale radiation-induced effects. Also, intrinsic DNA features, such as DNA topology and specific oligonucleotide sequences, strongly influence its response to damage from ionizing radiation. In this Account, we present our studies focused on the absolute quantification of photon- and low-energy electron-induced DNA damage in strategically selected target DNA sequences. Our methodology involves using DNA origami nanostructures, specifically the Rothemund triangle, as a platform to expose DNA sequences to either low-energy electrons or vacuum-ultraviolet (VUV, <15 eV) photons and subsequent atomic force microscopy (AFM) analysis. Through this approach, the effects of the DNA sequence, incorporation of halogenated radiosensitizers, DNA topology, and the radiation quality on radiation-induced DNA strand breakage have been systematically assessed and correlated with fundamental photon- and electron-driven mechanisms underlying DNA radiation damage. At lower energies, these mechanisms include dissociative electron attachment (DEA), where electrons attach to DNA molecules causing strand breaks, and dissociative photoexcitation of DNA. Additionally, further dissociative processes such as photoionization and electron impact contribute to the complex cascade of DNA damage events induced by ionizing radiation. We expect that emerging DNA origami-based approaches will lead to a paradigm shift in research fields associated with DNA damage and suggest future directions, which can foster the development of technological applications in nanomedicine, e.g., optimized cancer treatments or the molecular design of optimized radiosensitizing therapeutics.
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Daño del ADN , ADN , Nanotecnología , Humanos , ADN/química , ADN/efectos de la radiación , Daño del ADN/efectos de la radiación , Radiación IonizanteRESUMEN
DNA origami nanostructures are self-assembled into almost arbitrary two- and three-dimensional shapes from a long, single-stranded viral scaffold strand and a set of short artificial oligonucleotides. Each DNA strand can be functionalized individually using well-established DNA chemistry, representing addressable sites that allow for the nanometre precise placement of various chemical entities such as proteins, molecular chromophores, nanoparticles, or simply DNA motifs. By means of microscopic and spectroscopic techniques, these entities can be visualized or detected, and either their mutual interaction or their interaction with external stimuli such as radiation can be studied. This gives rise to the Lab-on-a-DNA origami approach, which is introduced in this Feature Article, and the state-of-the-art is summarized with a focus on light-harvesting nanoantennas and DNA platforms for single-molecule analysis either by optical spectroscopy or atomic force microscopy (AFM). Light-harvesting antennas can be generated by the precise arrangement of chromophores to channel and direct excitation energy. At the same time, plasmonic nanoparticles represent a complementary approach to focus light on the nanoscale. Plasmonic nanoantennas also allow for the observation of single molecules either by Raman scattering or fluorescence spectroscopy and DNA origami platforms provide unique opportunities to arrange nanoparticles and molecules to be studied. Finally, the analysis of single DNA motifs by AFM allows for an investigation of radiation-induced processes in DNA with unprecedented detail and accuracy.
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ADN de Forma A , Nanoestructuras , Nanotecnología/métodos , ADN/química , Nanoestructuras/química , Microscopía de Fuerza Atómica/métodos , Conformación de Ácido NucleicoRESUMEN
Ubiquinone molecules have a high biological relevance due to their action as electron carriers in the mitochondrial electron transport chain. Here, we studied the dissociative interaction of free electrons with CoQ0 , the smallest ubiquinone derivative with no isoprenyl units, and its fully reduced form, 2,3-dimethoxy-5-methylhydroquinone (CoQ0 H2 ), an ubiquinol derivative. The anionic products produced upon dissociative electron attachment (DEA) were detected by quadrupole mass spectrometry and studied theoretically through quantum chemical and electron scattering calculations. Despite the structural similarity of the two studied molecules, remarkably only a few DEA reactions are present for both compounds, such as abstraction of a neutral hydrogen atom or the release of a negatively charged methyl group. While the loss of a neutral methyl group represents the most abundant reaction observed in DEA to CoQ0 , this pathway is not observed for CoQ0 H2 . Instead, the loss of a neutral OH radical from the CoQ0 H2 temporary negative ion is observed as the most abundant reaction channel. Overall, this study gives insights into electron attachment properties of simple derivatives of more complex molecules found in biochemical pathways.
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Electrones , Hidrógeno , Aniones , Hidrógeno/química , IonesRESUMEN
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.
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We report absolute photoabsorption cross sections for gas-phase 2- and 5-bromopyrimidine in the 3.7-10.8 eV energy range, in a joint theoretical and experimental study. The measurements were carried out using high-resolution vacuum ultraviolet synchrotron radiation, with quantum chemical calculations performed through the nuclear ensemble approach in combination with time-dependent density functional theory, along with additional Franck-Condon Herzberg-Teller calculations for the first absorption band (3.7-4.6 eV). The cross sections of both bromopyrimidines are very similar below 7.3 eV, deviating more substantially from each other at higher energies. In the 7.3-9.0 eV range where the maximum cross-section is found, a single and broad band is observed for 5-bromopyrimidine, while more discernible features appear in the case of 2-bromopyrimidine. Several π* â π transitions account for the most intense bands, while weaker ones are assigned to transitions involving the nitrogen and bromine lone pairs, the antibonding σ*Br orbital, and the lower-lying Rydberg states. A detailed comparison with the available photo-absorption data of bromobenzene is also reported. We have found significant differences regarding the main absorption band, which is more peaked in bromobenzene, becoming broader and shifting to higher energies in both bromopyrimidines. In addition, there is a significant suppression of vibrational structures and of Rydberg states in the pair of isomers, most noticeably for 2-bromopyrimidine.
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Modelos Teóricos , Pirimidinas/química , Espectrofotometría Ultravioleta , Rayos Ultravioleta , Modelos Moleculares , Estructura Molecular , Fenómenos FísicosRESUMEN
In the search for alternatives to chlorine-containing gases, tetrafluoroethane, CF3CH2F (R134a), a widely used refrigerant gas, has been recognized as a promising substitute for dichlorodifluoromethane, CCl2F2 (R12). When R12 is replaced by R134a, the global warming potential drops from 8100 to 1430, the ozone depletion potential changes from 1 to 0, and the atmospheric lifetime decreases from 100 to 14 years. Electron interactions in the gas phase play a fundamental role in the atmospheric sciences. Here, we present a detailed study on electron-driven fragmentation pathways of CF3CH2F, in which we have investigated processes induced by both electron ionization and electron attachment. The measurements allow us to report the ion efficiency curves for ion formation in the energy range of 0 up to 25 eV. For positive ion formation, R134a dissociates into a wide assortment of ions, in which CF3+ is observed as the most abundant out of seven ions with a relative intensity above 2%. The results are supported by quantum chemical calculations based on bound state techniques, electron-impact ionization models, and electron-molecule scattering simulations, showing a good agreement. Moreover, the experimental first ionization potential was found at 13.10 ± 0.17 eV and the second at around 14.25 eV. For negative ion formation, C2F3- was detected as the only anion formed, above 8.3 eV. This study demonstrates the role of electrons in the dissociation of R134a, which is relevant for an improvement of the refrigeration processes as well as in atmospheric chemistry and plasma sciences.
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We investigate dissociative electron attachment to tirapazamine through a crossed electron-molecule beam experiment and quantum chemical calculations. After the electron is attached and the resulting anion reaches the first excited state, D1, we suggest a fast transition into the ground electronic state through a conical intersection with a distorted triazine ring that almost coincides with the minimum in the D1 state. Through analysis of all observed dissociative pathways producing heavier ions (90-161 u), we consider the predissociation of an OH radical with possible roaming mechanism to be the common first step. This destabilizes the triazine ring and leads to dissociation of highly stable nitrogen-containing species. The benzene ring is not altered during the process. Dissociation of small anionic fragments (NO2-, CN2-, CN-, NH2-, O-) cannot be conclusively linked to the OH predissociation mechanism; however, they again do not require dissociation of the benzene ring.
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Electrones , Tirapazamina/química , Algoritmos , Aniones/química , Modelos Químicos , Fármacos Sensibilizantes a Radiaciones/químicaRESUMEN
Nicotinamide (C6H6N2O) is a biologically relevant molecule. This compound has several important roles related to the anabolic and metabolic processes that take place in living organisms. It is also used as a radiosensitizer in tumor therapy. As a result of the interaction of high-energy radiation with matter, low-energy electrons are also released, which can also interact with other molecules, forming several types of ions. In the present investigation, dissociative electron attachment to C6H6N2O has been studied in a crossed electron-molecular beams experiment in the electron energy range of about 0-15 eV. In the experiment, six anionic species were detected: C6H5N2O-, C5H4N-, NCO-, O-/NH2 -, and CN-, with NCO- being the most prominent anion. We also provide detailed computational results regarding the energetic thresholds and pathways of the respective dissociative electron attachment (DEA) channels. The experimental results are compared with the theoretical ones and on this basis, the possible DEA reactions for the formation of anions at a given resonance energy were assigned as well as the generation of neutrals fragments such as pyridine and its several derivatives and radicals are predicted. The pyridine ring seems to stay intact during the DEA process.
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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.
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Nitroimidazoles are important compounds in medicine, biology, and the food industry. The growing need for their structural assignment, as well as the need for the development of the detection and screening methods, provides the motivation to understand their fundamental properties and reactivity. Here, we investigated the decomposition of protonated ronidazole [Roni+H]+ in low-energy and high-energy collision-induced dissociation (CID) experiments. Quantum chemical calculations showed that the main fragmentation channels involve intramolecular proton transfer from nitroimidazole to its side chain followed by a release of NH2CO2H, which can proceed via two pathways involving transfer of H+ from (1) the N3 position via a barrier of TS2 of 0.97 eV, followed by the rupture of the C-O bond with a thermodynamic threshold of 2.40 eV; and (2) the -CH3 group via a higher barrier of 2.77 eV, but with a slightly lower thermodynamic threshold of 2.24 eV. Electrospray ionization of ronidazole using deuterated solvents showed that in low-energy CID, only pathway (1) proceeds, and in high-energy CID, both channels proceed with contributions of 81% and 19%. While both of the pathways are associated with small kinetic energy release of 10-23 meV, further release of the NO⢠radical has a KER value of 339 meV.
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Interactions of low-energy electrons with the FEBID precursor Cr(CO)6 have been investigated in a crossed electron-molecular beam setup coupled with a double focusing mass spectrometer with reverse geometry. Dissociative electron attachment leads to the formation of a series of anions by the loss of CO ligand units. The bare chromium anion is formed by electron capture at an electron energy of about 9 eV. Metastable decays of Cr(CO)5- into Cr(CO)4-, Cr(CO)4- into Cr(CO)3- and Cr(CO)3- into Cr(CO)2- are discussed. Electron-induced dissociation at 70 eV impact energy was found to be in agreement with previous studies. A series of Cr(CO) n C+ (0 ≤ n ≤ 3) cations formed by C-O cleavage is described for the first time. The metastable decay of Cr(CO)6+ into Cr(CO)5+ and collision-induced dissociation leading to bare Cr+, are discussed. In addition, doubly charged cations were identified and the ration between doubly and singly charged fragments was determined and compared with previous studies, showing considerable differences.
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In this work, we report theoretical and experimental cross sections for elastic scattering of electrons by chlorobenzene (ClB). The theoretical integral and differential cross sections (DCSs) were obtained with the Schwinger multichannel method implemented with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR). The calculations with the SMCPP method were done in the static-exchange (SE) approximation, for energies above 12 eV, and in the static-exchange plus polarization approximation, for energies up to 12 eV. The calculations with the IAM-SCAR method covered energies up to 500 eV. The experimental differential cross sections were obtained in the high resolution electron energy loss spectrometer VG-SEELS 400, in Lisbon, for electron energies from 8.0 eV to 50 eV and angular range from 7(∘) to 110(∘). From the present theoretical integral cross section (ICS) we discuss the low-energy shape-resonances present in chlorobenzene and compare our computed resonance spectra with available electron transmission spectroscopy data present in the literature. Since there is no other work in the literature reporting differential cross sections for this molecule, we compare our theoretical and experimental DCSs with experimental data available for the parent molecule benzene.