EPR spectroscopy on irradiated nickel tetracyanide in NaCl host lattice: mechanism for the simultaneous formation of reduced and oxidized species

The kinetics of oxidized and reduced Ni²⁺ complexes produced by X-ray irradiation on single crystals of NaCl doped with [Ni(CN)₄]²⁻ is studied by Electron Paramagnetic Resonance at room temperature. The interdependent generation of these two complexes is attributed to migration of the charge compensating vacancy from the reduced to the oxidized complex in a reversible reaction. At higher X-ray doses, there is a predominant formation of the reduced complex.     

Heavy metal phosphate nanophases in silica: influence of radiolysis probed via f-electron state properties

We have assessed the feasibility of carrying out time- and wavelength-resolved laser-induced fluorescence measurements of radiation damage in glassy silica. The consequences of alpha decay of Es-253 in LaPO₄ nanophases embedded in silica were probed based on excitation of 5f states of Cm³⁺, Bk³⁺, and Es³⁺ ions. The recorded emission spectra and luminescence decays showed that alpha decay of Es-253 ejected Bk-249 decay daughter ions into the surrounding silica and created radiation damage within the LaPO₄ nanophases. This conclusion is consistent with predictions of an ion transport code commonly used to model ion implantation. Luminescence from the ⁶D_7/2 state of Cm³⁺was used as an internal standard. Ion-ion energy transfer dominated the dynamics of the observed emitting 5f states and strongly influenced the intensity of observed spectra. In appropriate sample materials, laser-induced fluorescence provides a powerful method for fundamental investigation of alpha-induced radiation damage in silica.     

Model Calculations of Radiation-Induced Damage in 1-Methyluracil:9-Ethyladenine

Detailed EPR and ENDOR experiments on the cocrystalline complex of 1-methyluracil:9-Ethyladenine (MUEA) have revealed that the major radiation-induced products observed at 10 K on MU are: MUEA1, a radical formed by net hydrogen abstraction from the N1-CH₃ methyl group, MUEA2, the MU radical anion, and MUEA3, the C5 H-addition radical. The following four products were observed on the adenine moiety at 10 K, MUEA4, the N3 protonated adenine anion, MUEA5, the native adenine cation, MUEA6, the amino deprotonated adenine cation, and MUEA7, the C8 H-addition radical formed by net H-addition to C8 of the adenine base. The geometries, energetics, and hyperfine properties of all possible radicals of MU and EA, the native anions and cations, as well as radicals formed via net hydrogen atom abstraction (deprotonated cations) or addition (protonated anions) were investigated theoretically. All systems were optimized using the hybrid Hartree–Fock–density functional theory functional B3LYP, in conjunction with the 6-31G(d,p) basis set of Pople and co-workers. Calculations of the anisotropic hyperfine couplings for all the radicals observed in MUEA are presented and are shown to compare favorably with the experimentally measured hyperfine couplings. The calculated ionizations potentials indicate that EA would be the preferred oxidation site. In MUEA, both the adenine cation and its N4-deprotonated derivative were observed. The calculated electron affinities indicate that MU would be the preferred reduction site. In MUEA radical, MUEA2 is a uracil reduction product, however the protonation state of this radical could not be determined experimentally. Calculations suggest that MUEA2 is actually the C4=O protonated anion.     

Voltammetric Behavior of the Alizarin Red S Interaction with DNA and Damage to DNA

The electrochemical behavior and the interaction of alizarin red S (ARS) with calf thymus DNA was investigated on a bare glassy carbon electrode (GCE) and DNA modified GCE (DNA/GCE), respectively. ARS showed a pair of redox peaks at ?0.445 V and ?0.414 V on a bare GCE. On addition of DNA into the ARS solution, the peak current of ARS decreased and the peak potential positively shifted, but without new redox peaks appeared. The ARS reduction peak current increased with immersion time on a DNA/GCE. The results showed that ARS could interact with DNA molecules by intercalative binding mode. The equilibrium constant, binding number and the ratio of binding constant for oxidized and reduced ARS forms were obtained. The DNA damage was directly detected by appearance of guanosine and adenosine bases oxidation signal. The influence of experimental conditions on DNA damage extent was discussed in detail.     

镍与生物

镍是一种稀有金属元素，也是动植物和人的必需营养微量元素。本文对镍的生物学功能及对有机体可能造成的损害进行了详细地阐述。     

A Novel Toxicological Evaluation of TiO2 Nanoparticles on DNA Structure0

TiO2 has been tested to be toxic to DNA under the photo-irradiation of ultraviolet A （UVA）. However, in the dark conditions, after several days of treatment with TiO2 in aqueous solution, the interaction between TiO2 and two types of DNA was detected and the mechanisms were studied by the methods of gel-electrophoresis, IR spectroscopy and TEM. The results showed that the DNA would be bound to TiO2; the ratio of binding was related to the concentration and the treating time; the mechanism of binding is related to phosphate groups of DNA. Besides, DNA with different structure showed different degree of binding. These findings showed a new possible way through which the TiO2 nanoparticles interact with DNA.     

短波段光学减反膜的溶胶-凝胶法制备及性能分析

 随着大型激光器的发展，对短波段减反膜的要求日益提高，其中钕玻璃激光三倍频（355nm）的减反射成为新的技术要点。采用溶胶-凝胶工艺合成SiO₂溶胶，采用提拉镀膜法制备纳米多孔SiO₂薄膜，薄膜厚度为75nm，折射率控制在1.22，镀制在石英基底上的薄膜其355nm波长的反射率仅为0.2%。通过氨处理工艺和薄膜的表面修饰，薄膜的抗磨擦性能和疏水性能大大提高，薄膜经过蘸有灰尘、乙醇的棉花球擦洗20次和50次后，透射率最大值仅分别降低0.13% 和 0.39%，与水珠的接触角达到110°。     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

Polypyridyl-Based Copper Phenanthrene Complexes: Combining Stability with Enhanced DNA Recognition

We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (K_app) rising from 10⁵ to 10⁷ m ⁻¹ with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin.     

Modification of the lunar surface by solar wind ion bombardment

Trivalent osmium ions are substitutionally incorporated into aqueous precipitates and melt-grown single crystals of AgBr and AgC1. The ions are distributed between three structurally inequivalent lattice sites in both salts. From epr studies, we have inferred that these sites are distinguished by the arrangement of charge-compensating silver ion vacancies in the two closest cation subshells. The most reasonable dopant-vacancy configurations have been deduced from the epr data. These configurations persist up to at least 300 K, and are compared with those observed in other trivalent metal ion doped systems.