Ring-Selective Fragmentation in the Tirapazamine Molecule upon Low-Energy Electron Attachment

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.     

Experimental and Theoretical Studies of Dissociative Electron Attachment to Metabolites Oxaloacetic and Citric Acids

In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3–9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.     

Low-Energy Electron Damage to Condensed-Phase DNA and Its Constituents

The complex physical and chemical reactions between the large number of low-energy (0–30 eV) electrons (LEEs) released by high energy radiation interacting with genetic material can lead to the formation of various DNA lesions such as crosslinks, single strand breaks, base modifications, and cleavage, as well as double strand breaks and other cluster damages. When crosslinks and cluster damages cannot be repaired by the cell, they can cause genetic loss of information, mutations, apoptosis, and promote genomic instability. Through the efforts of many research groups in the past two decades, the study of the interaction between LEEs and DNA under different experimental conditions has unveiled some of the main mechanisms responsible for these damages. In the present review, we focus on experimental investigations in the condensed phase that range from fundamental DNA constituents to oligonucleotides, synthetic duplex DNA, and bacterial (i.e., plasmid) DNA. These targets were irradiated either with LEEs from a monoenergetic-electron or photoelectron source, as sub-monolayer, monolayer, or multilayer films and within clusters or water solutions. Each type of experiment is briefly described, and the observed DNA damages are reported, along with the proposed mechanisms. Defining the role of LEEs within the sequence of events leading to radiobiological lesions contributes to our understanding of the action of radiation on living organisms, over a wide range of initial radiation energies. Applications of the interaction of LEEs with DNA to radiotherapy are briefly summarized.     

Rates of Electron Attachment to Aluminum Oxides in Air-Xenon Mixtures

This paper reports results from measurements of the electron concentration in wakes behind aluminum spherical models flying at velocities of 2–5 km/sec in air-xenon mixtures at a total pressure in the ballistic track of 20–100 torr. The heating of the models moving in the ballistic track and aluminum ablation from their surfaces were calculated. The rate constant of electron attachment to microparticles is found, and it is shown that it depends on the fraction of xenon in the mixture. The dependence of the coefficient of electron accommodation to the microparticle surface on the xenon concentration in the mixture is obtained and explained from a physical point of view.__________Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 3, pp. 65–73, May–June, 2005.     

Electron Attachment to 5-Fluorouracil: The Role of Hydrogen Fluoride in Dissociation Chemistry

We investigate dissociative electron attachment to 5-fluorouracil (5-FU) employing a crossed electron-molecular beam experiment and quantum chemical calculations. Upon the formation of the 5-FU⁻ anion, 12 different fragmentation products are observed, the most probable dissociation channel being H loss. The parent anion, 5-FU⁻, is not stable on the experimental timescale (~140 µs), most probably due to the low electron affinity of FU; simple HF loss and F⁻ formation are seen only with a rather weak abundance. The initial dynamics upon electron attachment seems to be governed by hydrogen atom pre-dissociation followed by either its full dissociation or roaming in the vicinity of the molecule, recombining eventually into the HF molecule. When the HF molecule is formed, the released energy might be used for various ring cleavage reactions. Our results show that higher yields of the fluorine anion are most probably prevented through both faster dissociation of an H atom and recombination of F⁻ with a proton to form HF. Resonance calculations indicate that F⁻ is formed upon shape as well as core-excited resonances.     

HF Formation through Dissociative Electron Attachment—A Combined Experimental and Theoretical Study on Pentafluorothiophenol and 2-Fluorothiophenol

In chemoradiation therapy, dissociative electron attachment (DEA) may play an important role with respect to the efficiency of the radiosensitizers used. The rational tailoring of such radiosensitizers to be more susceptive to DEA may thus offer a path to increase their efficiency. Potentially, this may be achieved by tailoring rearrangement reactions into the DEA process such that these may proceed at low incident electron energies, where DEA is most effective. Favorably altering the orbital structure of the respective molecules through substitution is another path that may be taken to promote dissociation up on electron capture. Here we present a combined experimental and theoretical study on DEA in relation to pentafluorothiophenol (PFTP) and 2-fluorothiophenol (2-FTP). We investigate the thermochemistry and dynamics of neutral HF formation through DEA as means to lower the threshold for dissociation up on electron capture to these compounds, and we explore the influence of perfluorination on their orbital structure. Fragment ion yield curves are presented, and the thermochemical thresholds for the respective DEA processes are computed as well as the minimum energy paths for HF formation up on electron capture and the underlying orbital structure of the respective molecular anions. We show that perfluorination of the aromatic ring in these compounds plays an important role in enabling HF formation by further lowering the threshold for this process and through favorable influence on the orbital structure, such that DEA is promoted. We argue that this approach may offer a path for tailoring new and efficient radiosensitizers.     

The Role of Low-Energy Electron Interactions in cis-Pt(CO)2Br2 Fragmentation

Platinum coordination complexes have found wide applications as chemotherapeutic anticancer drugs in synchronous combination with radiation (chemoradiation) as well as precursors in focused electron beam induced deposition (FEBID) for nano-scale fabrication. In both applications, low-energy electrons (LEE) play an important role with regard to the fragmentation pathways. In the former case, the high-energy radiation applied creates an abundance of reactive photo- and secondary electrons that determine the reaction paths of the respective radiation sensitizers. In the latter case, low-energy secondary electrons determine the deposition chemistry. In this contribution, we present a combined experimental and theoretical study on the role of LEE interactions in the fragmentation of the Pt(II) coordination compound cis-PtBr₂(CO)₂. We discuss our results in conjunction with the widely used cancer therapeutic Pt(II) coordination compound cis-Pt(NH₃)₂Cl₂ (cisplatin) and the carbonyl analog Pt(CO)₂Cl₂, and we show that efficient CO loss through dissociative electron attachment dominates the reactivity of these carbonyl complexes with low-energy electrons, while halogen loss through DEA dominates the reactivity of cis-Pt(NH₃)₂Cl₂.     

Electron Beam Induced Reduction of V2O5 Studied by Analytical Electron Microscopy

The reduction of V₂O₅ under electron irradiation was studied by means of electron energy-loss spectroscopy, electron diffraction, and high-resolution imaging. The decrease of spectral intensity of O 1s excitations indicates a preferential removal of oxygen. The observed chemical shifts of the V 2p_3/2 and V 2p_1/2 peaks reveal that V⁵⁺ is reduced to V²⁺. Electron diffraction and high-resolution imaging show a structural change from the orthorhombic V₂O₅ to cubic VO. The beam induced reduction is compared with thermal decomposition of V₂O₅.     

Total Electron Detachment and Induced Cationic Fragmentation Cross Sections for Superoxide Anion (O2−) Collisions with Benzene (C6H6) Molecules

In this study, novel experimental total electron detachment cross sections for O₂⁻ collisions with benzene molecules are reported for the impact energy range (10–1000 eV), as measured with a transmission beam apparatus. By analysing the positively charged species produced during the collision events, relative total ionisation cross sections were derived in the incident energy range of 160–900 eV. Relative partial ionisation cross sections for fragments with m/z ≤ 78 u were also given in this energy range. We also confirmed that heavier compounds (m/z > 78 u) formed for impact energies between 550 and 800 eV. In order to further our knowledge about the collision dynamics governing the fragmentation of such heavier molecular compounds, we performed molecular dynamics calculations within the framework of the Density Functional Theory (DFT). These results demonstrated that the fragmentation of these heavier compounds strongly supports the experimental evidence of m/z = 39–42, 50, 60 (u) cations formation, which contributed to the broad local maximum in the total ionisation observed from 550 to 800 eV. This work reveals the reactivity induced by molecular anions colliding with hydrocarbons at high energies, processes that can take place in the interstellar medium under various local conditions.     

CdTe纳米颗粒的制备及与GSH电子转移机制研究

以CdCl₂·2.5H₂O为镉源,TeO₂为碲源,水合肼为还原剂,利用共沉淀-还原法制备了CdTe纳米颗粒。采用扫描电镜、X射线衍射仪、激光拉曼光谱仪、傅里叶红外光谱仪和固体紫外-可见分光光度计对CdTe纳米颗粒的形貌、结构和光吸收性能进行表征。结果表明,水浴温度为80 ℃、水浴时间为6 h、烧结温度为400 ℃、烧结时间为2 h时制备的CdTe有较高的结晶度和较好的光吸收性。通过荧光光谱测试发现,CdTe溶液的荧光强度随谷胱甘肽(GSH)浓度的增加而增大,在0.005~0.8 mmol/L检测范围的检测极限(LOD)为0.004 mmol/L。该研究为制备CdTe荧光探测器提供了新技术,而且为解释GSH在CdTe溶液中的荧光响应提供了依据。     

Scanning Electron Microscopic Studies on the Failure of Rubber-to-Metal Bonded Composites

Scanning electron microscopic studies were conducted to evaluate the failure mechanism of rubber-to-metal bonded composites in the 90° peel test (ASTM D 429-B). It was found that when cohesive failure in rubber takes place, the composites, failing by stick-slip mode, show high peel strength. Moreover, in such cases, there exists a linear correlation between the peel strength and the crosslink density of the rubber vulcanizate.     

Going with the Electron Flow: Heme Electronic Structure and Electron Transfer in Cytochrome c

Heme is an essential and functionally versatile cofactor. Our understanding of how the environment of a heme in a protein tunes its function has benefited from spectroscopic and functional investigations of heme proteins and their variants with altered heme environments. Two properties of current interest are the conformation of the heme and hydrogen bonding to heme propionates. By combining nuclear magnetic resonance experiments and density functional theory calculations, both of these characteristics have been shown to influence the distribution of the singly occupied molecular orbital on the heme of ferricytochrome c, which affects coupling to redox partners and electron-transfer rates. In addition, heme conformation has been shown to tune reduction potential. These results reveal that subtle variations in heme conformation and in interactions with its propionates can have significant impacts on electron-transfer activity.     

Electron transfer processes at the surface of MoOx/SiO2 catalysts

EPR studies using naturally abundant and ⁹⁵Mo-enriched molybdenum have shown that reduced MoO _x /SiO₂catalysts with different dispersion of molybdenum provide a unique opportunity for molecular-level investigations of surface phenomena involved in the bonding to and activation of small molecules by oxide surfaces. Different types of electron transfer (ET) processes accompanying the activation of O₂and N₂O as well as the reactivity of O^-and CH₂OH transients with coadsorbed CH₃OH and O₂, respectively, have been identified. They include nondissociative and dissociative ET, surface intramolecular ET, and electroprotic transformation (ET coupled with proton transfer). In the case of methanol dehydrogenation it was found that if the reaction occurs on the MoO _x cluster centers, ET exhibits a complementary character, in contrast to isolated Mo centers where noncomplementary ET accompanied by migration of the hydroxymethyl intermediate is observed.     

电子束预处理对醋酯纤维降解性能的影响

利用电子束辐照对醋酯纤维进行预处理,研究电子束辐照对醋酯纤维结构、性质及生物降解性能的影响。通过扫描电镜、红外光谱、黏度测试等方法证明:电子束辐照使醋酯纤维表面产生刻蚀,纤维大分子链断裂,聚合度降低,提高了酯酶和纤维素酶对醋酯纤维的降解能力,且辐照剂量越大,处理后醋酯纤维生物降解性能越好。     

Imaging the Kidney with an Unconventional Scanning Electron Microscopy Technique: Analysis of the Subpodocyte Space in Diabetic Mice

Transmission electron microscopy (TEM) remains the gold standard for renal histopathological diagnoses, given its higher resolving power, compared with light microscopy. However, it imposes several limitations on pathologists, including longer sample preparation time and a small observation area. To overcome these, we introduced a scanning electron microscopy (SEM) technique for imaging resin-embedded semi-thin sections of renal tissue. We developed a rapid tissue preparation protocol for experimental models and human biopsies which, alongside SEM digital imaging acquisition of secondary electrons (SE–SEM), enables fast electron microscopy examination, with a resolution similar to that achieved by TEM. We used this unconventional SEM imaging approach to investigate the subpodocyte space (SPS) in BTBR ob/ob mice with type 2 diabetes. Analysis of semi-thin sections with secondary electrons revealed that the SPS had expanded in volume and covered large areas of the glomerular basement membrane, forming wide spaces between the podocyte body and the underlying filtering membrane. Our results show that SE–SEM is a valuable tool for imaging the kidney at the ultrastructural level, filling the magnification gap between light microscopy and TEM, and reveal that in diabetic mice, the SPS is larger than in normal controls, which is associated with podocyte damage and impaired kidney function.     

超临界CO_2预处理对UHMWPE纤维电子束辐照效果的影响

采用正交试验,研究了超临界CO_2预处理工艺(压力、温度、时间)对辐敏剂三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)渗入率及超高相对分子质量聚乙烯(UHMWPE)纤维凝胶含量和蠕变率的影响,并利用Minitab软件分析UHMWPE纤维凝胶含量和蠕变率与TMPTMA渗入率之间的关系,最后通过对UHMWPE纤维各项性能的测定,进一步优化超临界CO_2预处理工艺。研究结果表明:处理温度对TMPTMA的渗入率及UHMWPE纤维凝胶含量和蠕变率影响最大,其次为压力,时间的影响最小;确定了最佳工艺为处理压力30 MPa、温度80℃、时间50 min;TMPTMA渗入率是引起各个影响因素不同水平之间凝胶含量和蠕变率出现差别的重要因素;超临界CO_2预处理对UHMWPE纤维的辐照交联起到了重要的促进作用,使其抗蠕变性能得到很大程度的改善。     

Real Space and Wave‐Number Space Studies of the Phase Structure and Morphology of iPP/PEOc Blends Using Scanning Electron Microscopy

The influence of blend composition on the phase structure and morphology of poly(propylene)/poly(ethylene‐co‐octene) blends was studied using SEM. A diameter d_g was defined and calculated in real space to discuss the phase structure and morphology of iPP/PEOc blends. The figure‐estimation method was introduced to determine the distribution width of d_g. It was shown that the distribution of d_g obeys a log‐normal distribution and the distribution width σ of d_g was calculated. In wave‐number (h) space, the correlation distance, a_c, was defined by applying light scattering theory to power spectrum images obtained by 2D Fourier transformation. Moreover, a fractal dimension, D_c, was introduced to describe the uniformity of the spatial distribution.

     

Spectral Probe for Electron Transfer and Addition Reactions of Azide Radicals with Substituted Quinoxalin-2-Ones in Aqueous Solutions

The azide radical (N₃^●) is one of the most important one-electron oxidants used extensively in radiation chemistry studies involving molecules of biological significance. Generally, it was assumed that N₃^● reacts in aqueous solutions only by electron transfer. However, there were several reports indicating the possibility of N₃^● addition in aqueous solutions to organic compounds containing double bonds. The main purpose of this study was to find an experimental approach that allows a clear assignment of the nature of obtained products either to its one-electron oxidation or its addition products. Radiolysis of water provides a convenient source of one-electron oxidizing radicals characterized by a very broad range of reduction potentials. Two inorganic radicals (SO₄^●−, CO₃^●−) and Tl²⁺ ions with the reduction potentials higher, and one radical (SCN)₂^●− with the reduction potential slightly lower than the reduction potential of N₃^● were selected as dominant electron-acceptors. Transient absorption spectra formed in their reactions with a series of quinoxalin-2-one derivatives were confronted with absorption spectra formed from reactions of N₃^● with the same series of compounds. Cases, in which the absorption spectra formed in reactions involving N₃^● differ from the absorption spectra formed in the reactions involving other one-electron oxidants, strongly indicate that N₃^● is involved in the other reaction channel such as addition to double bonds. Moreover, it was shown that high-rate constants of reactions of N₃^● with quinoxalin-2-ones do not ultimately prove that they are electron transfer reactions. The optimized structures of the radical cations (7-R-3-MeQ)^●+, radicals (7-R-3-MeQ)^● and N₃^● adducts at the C2 carbon atom in pyrazine moiety and their absorption spectra are reasonably well reproduced by density functional theory quantum mechanics calculations employing the ωB97XD functional combined with the Dunning’s aug-cc-pVTZ correlation-consistent polarized basis sets augmented with diffuse functions.     

Atomic Resolution Transmission Electron Microscopy of the Intergranular Structure of a Y2O3-Containing Silicon Nitride Ceramic

High-resolution transmission electron microscopy (HRTEM) employing focus-variation phase-reconstruction methods is used to image the atomic structure of grain boundaries in a silicon nitride ceramic at subangstrom resolution. Complementary energy-dispersive X-ray emission spectroscopy experiments revealed the presence of yttrium ions segregated to the 0.5–0.7-nm thin amorphous boundary layers that separate individual grains. Our objective here is probing if yttrium ions attach to the prismatic planes of the Si₃N₄ at the interface toward the amorphous layer, using Scherzer and phase-reconstruction imaging, as well as image simulation. Crystal structure images of grain boundaries in thin sample (<100 Å) areas do not reveal the attachment of yttrium at these positions, although lattice images from thicker areas do suggest the presence of yttrium at these sites. It is concluded that most of the yttrium atoms are located in the amorphous phase and only a few atoms may attach to the terminating prism plane. In this case, the line concentrations of such yttrium in the latter location are estimated to be at most one yttrium atom every 17 Å.     

Studies on the inhomogeneous nature of the silent discharge reactor: Part 2. kinetic simulation of a differential batch reactor

The silent discharge reactor is characterised by a large number of randomly distributed discrete primary reaction zones (PRZ). These are transient in nature. Primary electron-molecule collisions take place here with subsequent quenching of the atom-molecule or free radical-molecule processes. A model of a differential batch ozonizer has been proposed to study the influence of various forms of current pulse train, and the chemical activity of dielectric surface. The effect of multiple exposure of the reaction products to a series of electron avalanches has been evaluated. Finally the effects of temperature field and electron concentration within the electron avalanches have been studied.