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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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2-Bromo-1-(3,3-dinitroazetidin-1-yl)ethan-1-one (RRx-001) is a hypoxic cell chemotherapeutics with already demonstrated synergism in combined chemo-radiation therapy. The interaction of the compound with secondary low-energy electrons formed in large amounts during the physico-chemical phase of the irradiation may lead to these synergistic effects. The present study focuses on the first step of RRx-001 interaction with low-energy electrons in which a transient anion is formed and fragmented. Combination of two experiments allows us to disentangle the decay of the RRx-001 anion on different timescales. Sole presence of the electron initiates rapid dissociation of NO2 and HNO2 neutrals while NO2- and Br- anions are produced both directly and via intermediate complexes. Based on our quantum chemical calculations, we propose that bidirectional intersystem crossing between π*(NO2) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well.

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8-Thiomethyladenine (ASCH3), a potentially radiosensitizing modified nucleobase, has been synthesized in a reaction between 8-thioadenine and methyl iodide. Despite favorable dissociative electron attachment (DEA) characteristics, the radiolysis of an aqueous solution of ASCH3 with a dose of X-ray amounting to as much as 300 Gy leads to no effects. Nevertheless, crossed electron-molecule beam experiments in the gas phase on ASCH3 confirm the theoretical findings regarding the stability of its radical anion, namely, the most abundant reaction channel is related to the dissociation of the S-CH3 bond in the respective anion. Furthermore, electron-induced degradation of ASCH3 has been observed in aprotic acetonitrile, which is strong evidence for the involvement of proton transfer (PT) in stabilizing the radical anion in an aqueous solution. These findings demonstrate that PT in water can be the main player in deciding the radiosensitizing properties of modified nucleobases/nucleosides.

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In the search for effective radiosensitizers for tumor cells, halogenated uracils have attracted more attention due to their large cross section for dissociation upon the attachment of low-energy electrons. In this study, we investigated dissociative electron attachment (DEA) to 5-iodo-4-thio-2'-deoxyuridine, a potential radiosensitizer using a crossed electron-molecule beam experiment coupled with quadrupole mass spectrometry. The experimental results were supported by calculations on the threshold energies of formed anions and transition state calculations. We show that low-energy electrons with kinetic energies near 0 eV may effectively decompose the molecule upon DEA. The by far most abundant anion observed corresponds to the iodine anion (I-). Due to the associated bond cleavage, a radical site is formed at the C5 position, which may initiate strand break formation if the molecule is incorporated into a DNA strand. Our results reflect the conclusion from previous radiolysis studies with the title compound, suggesting its potential as a radiosensitizer.

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Compounds based on nitrotriazole have been studied for their application as potential radiosensitizers for the treatment of tumors and as energetic materials. In the former application, the initial reduction of the compounds may serve as a mechanism which leads to the formation of tumor-active species. In this study, we investigated the fundamental properties of anion formation in isolated 3-nitro-1,2,4-triazole (3NTR) molecules upon attachment of low-energy electrons. The resulting product anions formed were detected via mass spectrometry. Quantum chemical calculations were performed to study the dissociation pathways and to derive the threshold energies. We also studied the attachment of electrons to the native 1H-1,2,4-triazole (TR) molecule, revealing the influence of the nitro group on anion formation. Comparing the results for these two systems, we computationally observed a considerable more stable parent anion for 3NTR, which results in significantly more effective degradation of the molecule at lower electron energies. Although characteristic fragmentation reactions in the presence of the nitro group were observed (like formation of NO2- or the release of an OH radical), the main dissociation channel for the 3NTR anion turned out to be the direct dissociation of a hydrogen radical by a single bond cleavage, which we also observed for TR as the main channel. Thus, the triazole ring shows a pronounced stability against electron attachment-induced cleavage compared, for example, to the imidazole ring, which is found in common nitroimidazolic radiosensitizers.

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When modified uridine derivatives are incorporated into DNA, radical species may form that cause DNA damage. This category of molecules has been proposed as radiosensitizers and is currently being researched. Here, we study electron attachment to 5-bromo-4-thiouracil (BrSU), a uracil derivative, and 5-bromo-4-thio-2'-deoxyuridine (BrSdU), with an attached deoxyribose moiety via the N-glycosidic (N1-C) bond. Quadrupole mass spectrometry was used to detect the anionic products of dissociative electron attachment (DEA), and the experimental results were supported by quantum chemical calculations performed at the M062X/aug-cc-pVTZ level of theory. Experimentally, we found that BrSU predominantly captures low-energy electrons with kinetic energies near 0 eV, though the abundance of bromine anions was rather low compared to a similar experiment with bromouracil. We suggest that, for this reaction channel, proton-transfer reactions in the transient negative ions limit the release of bromine anions.

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Single-strand breaks (SSBs) induced via electron attachment were previously observed in dry DNA under ultrahigh vacuum (UHV), while hydrated electrons were found not able to induce this DNA damage in an aqueous solution. To explain these findings, crossed electron-molecular beam (CEMB) and anion photoelectron spectroscopy (aPES) experiments coupled to density functional theory (DFT) modeling were used to demonstrate the fundamental importance of proton transfer (PT) in radical anions formed via electron attachment. Three molecular systems were investigated: 5'-monophosphate of 2'-deoxycytidine (dCMPH), where PT in the electron adduct is feasible, and two ethylated derivatives, 5'-diethylphosphate and 3',5'-tetraethyldiphosphate of 2'-deoxycytidine, where PT is blocked due to substitution of labile protons with the ethyl residues. CEMB and aPES experiments confirmed the cleavage of the C3'/C5'-O bond as the main dissociation channel related to electron attachment in the ethylated derivatives. In the case of dCMPH, however, electron attachment (in the aPES experiments) yielded its parent (intact) radical anion, dCMPH-, suggesting that its dissociation was inhibited. The aPES-measured vertical detachment energy of the dCMPH- was found to be 3.27 eV, which agreed with its B3LYP/6-31++G(d,p)-calculated value and implied that electron-induced proton transfer (EIPT) had occurred during electron attachment to the dCMPH model nucleotide. In other words, EIPT, subduing dissociation, appeared to be somewhat protective against SSB. While EIPT is facilitated in solution compared to the dry environment, the above findings are consistent with the stability of DNA against hydrated electron-induced SSB in solution versus free electron-induced SSB formation in dry DNA.

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It has been debated for years if the polycyclic aromatic hydrocarbon phenanthrene exists in its anionic form, or, in other words, if its electron affinity (EA) is positive or negative. In this contribution we confirm that the bare phenanthrene anion Ph- created in a binary collision with an electron at room temperature has a lifetime shorter than microseconds. However, the embedding of neutral phenanthrene molecules in negatively charged helium nanodroplets enables the formation of phenanthrene anions by charge transfer processes and the stabilization of the latter in the ultracold environment. Gentle shrinking of the helium matrix of phenanthrene-doped HNDs by collisions with helium gas makes the bare Ph- visible by high-resolution mass spectrometry. From these and previous measurements we conclude, that the EA of phenanthrene is positive and smaller than 24.55 meV.

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Radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well-defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side-reactions and high spatio-temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low-energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C-S bond is induced upon low-energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (. CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.

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Fluoroscopy-guided placement of pedicle screws is usually used to position pedicle screws, although it is highly risky due to lack of accuracy during operation and surgeon's intensive labor requirement during surgery. In this study, a new method was introduced to consider the issues and we tried to reduce the risk of pedicle screw placement and drilling process. To put pedicle screws in the correct position and orientation, a specific drill guide is designed and fabricated by additive manufacturing technology. In addition, since the drilling process is remarkably important and it is usually dependent on surgeon skill, therefore a teleoperation system is proposed to perform this task. In order to let the surgeon to have better control on the patient, a control scheme including position and velocity signals along with surgeon force and reaction force of vertebra was proposed. This helped the surgeon for proper control on the patient during surgery. A force estimation algorithm was presented to eliminate measuring external force signal. Consequently, 10 vertebras were used to evaluate specific drill guide and teleoperation system simultaneously. Then, the computed tomography evaluation demonstrated that Kirschner wire trajectories followed the planned axes with an error between 1 and 2 mm in 20% of cases and less than 1 mm in 80% of cases. The results obtained by the teleoperation system showed that the surgeon, in the master side, has proper control over the patient body in the slave side because the slave robot followed the master position. Furthermore, the surgeon in the master side sensed the reaction force of vertebra in the slave side appropriately.

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The need for simple and reliable means of respiratory monitoring has existed since the beginnings of medicine. In the present study, we describe the use of color spectrographic analysis of breathing sounds recorded from the external ear canal as a candidate technology to meet this need. A miniature electret microphone was modified with the addition of an adapter to allow it to be placed comfortably in the external ear canal. The amplified signal was then connected to a real-time color spectrogram program running on a laptop personal computer utilizing the Windows operating system. Based on the results obtained, we hypothesize that the real-time display of color spectrogram breathing patterns locally or at a central monitoring station may turn out to be a useful means of respiratory monitoring in patients at increased risk of respiratory depression or other respiratory problems. Finally, we conducted a statistical analysis that suggests that significant spectrogram differences may exist among some groups investigated in the study.

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