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At least 109 records · Page 6

High- and low-LET induced chromosome damage in human lymphocytes: a time-course of aberrations in metaphase and interphase

PURPOSE: To investigate how cell-cycle delays in human peripheral lymphocytes affect the expression of complex chromosome damage in metaphase following high- and low-LET radiation exposure. MATERIALS AND METHODS: Whole blood was irradiated in vitro with a low and a high dose of 1 GeV u(-1) iron particles, 400MeV u(-1) neon particles or y-rays. Lymphocytes were cultured and metaphase cells were collected at different time points after 48-84h in culture. Interphase chromosomes were prematurely condensed using calyculin-A, either 48 or 72 h after exposure to iron particles or gamma-rays. Cells in first division were analysed using a combination of FISH whole-chromosome painting and DAPI/ Hoechst 33258 harlequin staining. RESULTS: There was a delay in expression of chromosome damage in metaphase that was LET- and dose-dependant. This delay was mostly related to the late emergence of complex-type damage into metaphase. Yields of damage in PCC collected 48 h after irradiation with iron particles were similar to values obtained from cells undergoing mitosis after prolonged incubation. CONCLUSION: The yield of high-LET radiation-induced complex chromosome damage could be underestimated when analysing metaphase cells collected at one time point after irradiation. Chemically induced PCC is a more accurate technique since problems with complicated cell-cycle delays are avoided.

Non-NASA Center

Oxidation of SiC Fiber-Reinforced SiC Matrix Composites with a BN Interphase

SiC-fiber reinforced SiC matrix composites with a BN interphase were oxidized in reduced oxygen partial pressures of oxygen to simulate the environment for hypersonic vehicle leading edge applications. The constituent fibers as well as composite coupons were oxidized in oxygen partial pressures ranging from 1000 ppm O2 to 5% O2 balance argon. Exposure temperatures ranged from 816 C to 1353 C (1500 F to 2450 F). The oxidation kinetics of the coated fibers were monitored by thermogravimetric analysis (TGA). An initial rapid transient weight gain was observed followed by parabolic kinetics. Possible mechanisms for the transient oxidation are discussed. One edge of the composite coupon seal coat was ground off to simulate damage to the composite which allowed oxygen ingress to the interior of the composite. Oxidation kinetics of the coupons were characterized by scanning electron microscopy since the weight changes were minimal. It was found that sealing of the coupon edge by silica formation occurred. Differences in the amount and morphology of the sealing silica as a function of time, temperature and oxygen partial pressure are discussed. Implications for use of these materials for hypersonic vehicle leading edge materials are summarized.

Opila, Elizabeth

Proximity Within Interphase Chromosome Contributes to the Breakpoint Distribution in Radiation-Induced Intrachromosomal Exchanges

Previously, we reported that breaks involved in chromosome aberrations were clustered in several regions of chromosome3 in human mammary epithelial cells after exposures to either low-or high-LET radiation. In particular, breaks in certain regions of the chromosome tended to rejoin with each other to form an intrachromosome exchange event. This study tests the hypothesis that proximity within a single chromosome in interphase cell nuclei contributes to the distribution of radiation-induced chromosome breaks. Chromosome 3 in G1 human mammary epithelial cells was hybridized with the multicolor banding in situ hybridization (mBAND) probes that distinguish the chromosome in six differently colored regions, and the location of these regions was measured with a laser confocal microscope. Results of the study indicated that, on a multi-mega base pair scale of the DNA, the arrangement of chromatin was non-random. Both telomere regions tended to be located towards the exterior of the chromosome domain, whereas the centromere region towards the interior. In addition, the interior of the chromosome domain was preferentially occupied by the p-arm of the chromatin, which is consistent with our previous finding of intrachromosome exchanges involving breaks on the p-arm and in the centromere region of chromosome3. Other factors, such as the fragile sites in the 3p21 band and gene regulation, may also contribute to the breakpoint distribution in radiation-induced chromosome aberrations. Further investigations suggest that the 3D chromosome folding is cell type and culture condition dependent.

Zhang, Ye

The Chemistry, Formation and Passivation of Solid-Electrolyte Interphase (SEI) from FSI- Breakdown at Li-metal Potential

LiFSI-based liquid electrolytes are promising for realizing high Coulombic efficiency (CE) and long cycle life of next-generation high-energy Li metal battery. Nevertheless, the fundamentals of both the chemistry and formation of solid-electrolyte interphase (SEI) in these electrolytes have remained elusive. Herein, we extensively combine electrochemistry and X-ray photoelectron spectroscopy (XPS) to illustrate the reaction pathways of electrolyte decomposition, especially FSI- breakdown, as well as the dissolution trend of various inorganic SEI components. The SEI-forming reactions at Cu/electrolyte interface manifest a potential (E) dependence, driven by direct electron-transfer (ET) and Li underpotential-deposition (Li UPD) at high and low E regions, respectively. By closely correlating the XPS data obtained with and without solvent washing, we demonstrate that not all the products derived from SEI reactions are incorporated into forming a passivating surface layer, with a notable portion dissolving into liquid electrolyte instead. Importantly, high-CE electrolyte dictated by the chemical identity of solvent, is found to exhibit minimized interfacial reactivity of SEI formation enabling more effective interphasial passivation, via preferential integration of passivating ingredients such as LiF. Overall, this work formulates a systematic understating of bridging the SEI chemistry, formation and passivation while identifying key characteristics of high-performance electrolyte for guiding future design.

Bao, Zhenan [SLAC National Accelerator Laboratory

Machine-Learning-Guided Insights into Solid-Electrolyte Interphase Conductivity: Are Amorphous Lithium Fluorophosphates the Key?

Despite decades of study, the identity of the dominant Li + -conducting phase within the inorganic SEI of Li-ion batteries remains unresolved. While the mosaic model describes LiF/Li 2 O/Li 2 CO 3 nanocrystallites within a disordered matrix, these crystalline phases inherently offer limited ionic conductivity. Growing evidence suggests that interfaces, grain boundaries, and amorphous phases may instead host the primary fast-ion pathways. Using diffusion-based generative structure prediction and machine-learning interatomic potentials (MLIPs), we investigate lithium difluorophosphate (LiPO 2 F 2 ), a key mixed-anion decomposition product of phosphorus- and fluorine-containing electrolytes. We identify a stable crystalline polymorph and demonstrate that the amorphous counterpart is conductive, with projected room-temperature σ ≈ 0.18 mS cm –1 and E a ≈ 0.40 eV. Here, this enhancement stems from structural disorder flattening the Li site-energy landscape and a low formation energy for Li-interstitial defects, which supplies additional mobile carriers. We propose amorphous mixed-anion Li-P-O-F phases as a promising conducting medium in the SEI, offering a specific target for engineering improved battery interfaces.

Zhong, Peichen [University of California, Berkeley

Solid-state prealkylation of electrode architectures to tune solid electrolyte interphase composition

Efficient electrochemical cycling of certain Si anodes is limited by irreversible Li consumption to form and continually reform the solid electrolyte interface (SEI) due to Si expansion/contraction and fracture. Prelithiation can compensate for these losses; however, the starting open circuit potential (VOC) becomes highly reducing and, therefore, the electrolyte reduction chemistry that influences the SEI composition can change. Herein, we compare SEI formation for electrodes prelithiated using Solid State Prealkylation of Electrode Architectures (SPEAR) versus traditional electrochemically lithiated architectures (ECLAR), focusing on SEI compositional changes as a function of stoichiometry (0.28 ≤ x ≤ 1.38 in LixSi). Increasing SPEAR prelithiation decreased the initial VOC of Si anodes vs. Li/Li+ from ∼3 V (Li0.28Si) to < 0.5 V for Li1.38Si, enabling simultaneous competitive reduction of EC, EMC, and LiPF6 at low potentials. Ex situ7Li and 29Si cross-polarization NMR and XPS reveal that SPEAR drives thicker SEI formation with substantially increased P/F contributions and a predominantly inorganic insoluble SEI (71.4% inorganic for Li1.38Si), consistent with accelerated LiPF6-derived POx/LiPFx/LiF formation relative to ECLAR analogs which exhibit carbonate-rich organic SEI compositions. Symmetric-cell EIS further indicates SPEAR-specific impedance features consistent with pore reduction (filling) during LixSi formation. In full cells, SPEAR prelithiation increases the initial coulombic efficiency (ICE) and accelerates SEI formation and stabilization with Li1.38Si reaching 99.4% coulombic efficiency (CE) by cycle 2.

Musgrove, Amanda [ORNL] (ORCID:0009000220910389)

Atomistic Modeling of the Interphase Structure between Alumina and Al12Fe2Cr Quasicrystal Approximant

Molecular dynamics simulations are performed to study the stability of an fcc metallic interlayer phase between an iron aluminide quasicrystal approximant (QCA) phase (84.2 Al, 5.7 Fe, 5.4 Ni, and 4.7 at.% Cr) and aluminum oxides (α-Al 2 O 3 and γ-Al 2 O 3 ). The presence of the interlayer phase was experimentally observed in some regions of the inner diameter surface of a TPBAR cladding tube. The simulations employed existing many-body (MEAM and EAM) interatomic potentials to describe atomic interactions in the interlayer and QCA phases, and Buckingham+Coulomb pair interactions for the alumina and between the alumina and the QCA (or fcc). Interface systems of QCA/alumina, fec/alumina, and QCA/fcc are modeled and the fracture energy of the interfaces is calculated. Based on the fracture energies, for the γ-Al 2 O 3 , both MEAM and EAM suggest that the fcc interlayer phase would not form. For the α-Al 2 O 3 , the MEAM predicts that the fcc phase would form, however, the EAM predicts that it forms only if the α-Al 2 O 3 is Al-terminated at the interface. For the O-terminated α-Al 2 O 3 , the EAM predicts the fcc phase would not form, consistent with the results for γ-Al 2 O 3 .

36 MATERIALS SCIENCE

Glassy interphases reinforce elastomeric nanocomposites by enhancing percolation-driven volume expansion under strain

For nearly a century, introduction of nanoparticles to elastomers has yielded extraordinarily tough nanocomposites that are critical to technologies from actuators to tires. The mechanisms by which this reinforcement occurs have nevertheless remained a central open question in material science. One widely debated hypothesis posits that strong interactions between polymer and particles induce "glassy bridges" that cement particles into a cohesive percolating network that resists elongation. Here, molecular dynamics simulations show that glassy particle shells do not primarily provide elongational cohesion. Instead, they amplify an underlying mechanism wherein competition between filler and elastomer networks causes the elastomer's volume to increase on deformation. This induces contributions from the elastomer's bulk modulus, which is of order 1000 times larger than its Young's modulus. These findings establish a unified understanding of low-strain reinforcement in filled elastomers as emanating from volumetric competition between coexisting particulate and elastomeric networks. This reframes and unifies our understanding of low-strain reinforcement, provides a clear-cut diagnostic for the presence of glassy bridging, and offers a new design principle for tough elastomeric nanocomposites.

Computational Physics (physics.comp-ph)

Composite Property Dependence on the Fiber, Matrix, and the Interphase

The matrix properties of a difunctional epoxy, Epon 828, were varied. The Hercules type A fiber was also utilized in this investigation. The fiber and the interface between fiber and matrix were examined in terms of shear strength. Micrographs of the epoxy matrix are presented.

Drzal, L. T.