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Li, Lin

Publications and source records attributed to Li, Lin.

47 records · Page 3

In situ indentation and high cycle tapping deformation responses in a nanolaminate crystalline/amorphous metal composite

The incorporation of nanostructured and amorphous metals into modern applications is reliant on the understanding of deformation and failure modes in constrained conditions. To study this, a 105 nm crystalline Cu/160 nm amorphous Cu 45 Zr 55 (at.%) multilayer structure was fabricated with the two crystalline layers sputter deposited between the top-middle-bottom amorphous layers and prepared to electron transparency. The multilayer was then in situ indented either under a single load to a depth of ~ 100 nm (max load of ~ 100 μN) or held at 20 μN and then repeatedly indented with an additional 5 μN up to 20,000 cycles in a transmission electron microscope to compare the deformation responses in the nanolaminate. For the single indentation test, the multilayer showed serrated load-displacement behavior upon initial indentation inductive of shear banding. Additionally, at an indentation depth of ~ 32 nm, the multilayer exhibited perfect plastic behavior and no strain hardening. Both indented and fatigue-indented films revealed diffraction contrast changes with deformation. Subsequent Automated Crystal Orientation Mapping (ACOM) measurements confirmed and quantified global texture changes in the crystalline layers with specifically identified grains revealing rotation. Using a finite element model, the in-plane displacement vectors under the indent mapped conditions where ACOM determined grain rotation was observed, indicating the stress flow induced grain rotation. Furthermore, the single indented Cu layers also exhibited evidence of deformation induced grain growth, which was not evident in the fatigue-indented Cu based multilayer. Finally, the single indented multilayer retained a significant plastic crater in the upper most amorphous layer that directly contacted the indenter; a negligible crater impression in the same region was observed in the fatigued tested multilayer. These differences are explained by the different loading methods, applied load, and deformation mechanisms experienced in the multilayers.

36 MATERIALS SCIENCE↗

The CCR4‐NOT complex component NOT1 regulates RNA‐directed DNA methylation and transcriptional silencing by facilitating Pol IV‐dependent siRNA production

Summary Small interfering RNAs (siRNAs) are responsible for establishing and maintaining DNA methylation through the RNA‐directed DNA methylation (RdDM) pathway in plants. Although siRNA biogenesis is well known, it is relatively unclear about how the process is regulated. By a forward genetic screen in Arabidopsis thaliana , we identified a mutant defective in NOT1 and demonstrated that NOT1 is required for transcriptional silencing at RdDM target genomic loci. We demonstrated that NOT1 is required for Pol IV‐dependent siRNA accumulation and DNA methylation at a subset of RdDM target genomic loci. Furthermore, we revealed that NOT1 is a constituent of a multi‐subunit CCR4‐NOT deadenylase complex by immunoprecipitation combined with mass spectrometry and demonstrated that the CCR4‐NOT components can function as a whole to mediate chromatin silencing. Therefore, our work establishes that the CCR4‐NOT complex regulates the biogenesis of Pol IV‐dependent siRNAs, and hence facilitates DNA methylation and transcriptional silencing in Arabidopsis.

Zhou, Hao‐Ran↗

Photo–thermo Catalytic Oxidation over a TiO 2 ‐WO 3 ‐Supported Platinum Catalyst

Abstract Photo–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo‐ and photocatalytic perspectives. Deep insights into photo–thermo catalysis are achieved via the catalytic oxidation of propane (C 3 H 8 ) over a Pt/TiO 2 ‐WO 3 catalyst that severely suffers from oxygen poisoning at high O 2 /C 3 H 8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C 3 H 8 lowers to a record‐breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol −1 to 11 kJ mol −1 . Furthermore, the reaction order of O 2 is −1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in‐situ‐captured reaction intermediates.

Kang, Leilei↗

Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers

Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN) 4 (2,2'-bipyridine)] 2- (1), [Fe(CN) 4 (2,3-bis(2-pyridyl)pyrazine)] 2- (2) and [Fe(CN) 4 (2,2'-bipyrimidine)] 2- (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the 1 MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the 3 MLCT lifetime to range from 180 fs to 67 ps. The 3 MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred ( 3 MC) excited state, as established by the Tanabe–Sugano analysis of the Fe 2p3d RIXS data. In contrast, the 3 MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing 3 MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The 3 MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm -1 ), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the 3 MLCT and the 3 MC states and suppression of the intramolecular distortion of the acceptor ligand in the 3 MLCT excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photo–thermo Catalytic Oxidation over a TiO 2 -WO 3 -Supported Platinum Catalyst

Photo–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo- and photocatalytic perspectives. Deep insights into photo–thermo catalysis are achieved via the catalytic oxidation of propane (C 3 H 8 ) over a Pt/TiO 2 -WO 3 catalyst that severely suffers from oxygen poisoning at high O 2 /C 3 H 8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C 3 H 8 lowers to a record-breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol -1 to 11 kJ mol -1 . Furthermore, the reaction order of O 2 is -1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in-situ-captured reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uninstalled Performance Predictions of a Magnesium-Fueled Ramjet Cycle in Carbon Dioxide Atmospheres

Evaluation of alternative propulsion cycles for planetary space exploration applications is motivated by ongoing emphasis of robotic science and human exploration missions and concepts. Atmosphere-breathing propulsion systems operating on their own or in a combined cycle with other engines offer the potential to increase overall propulsion efficiency and reduce the amount of propellant that must be carried on board the vehicle. The purpose of this paper is to evaluate the idealized uninstalled performance characteristics of metal-fueled ramjet systems operating in carbon dioxide atmospheres. Physics-based predictions are presented for critical and a range of supercritical conditions of the propulsion cycle.

Axdahl, Erik L.↗

Estimating Surface Soil Moisture in Simulated AVIRIS Spectra

Soil albedo is influenced by many physical and chemical constituents, with moisture being the most influential on the spectra general shape and albedo (Stoner and Baumgardner, 1981). Without moisture, the intrinsic or matrix reflectance of dissimilar soils varies widely due to differences in surface roughness, particle and aggregate sizes, mineral types, including salts, and organic matter contents. The influence of moisture on soil reflectance can be isolated by comparing similar soils in a study of the effects that small differences in moisture content have on reflectance. However, without prior knowledge of the soil physical and chemical constituents within every pixel, it is nearly impossible to accurately attribute the reflectance variability in an image to moisture or to differences in the physical and chemical constituents in the soil. The effect of moisture on the spectra must be eliminated to use hyperspectral imagery for determining minerals and organic matter abundances of bare agricultural soils. Accurate soil mineral and organic matter abundance maps from air- and space-borne imagery can improve GIS models for precision farming prescription, and managing irrigation and salinity. Better models of soil moisture and reflectance will also improve the selection of soil endmembers for spectral mixture analysis.

Whiting, Michael L.↗

Nonlinear Spectral Mixture Modeling of Lunar Multispectral: Implications for Lateral Transport

Linear and nonlinear spectral mixture models applied to Clementine multispectral images of the Moon result in roughly similar spatial distributions of endmember abundances. However, there are important differences in the absolute values of the predicted abundances. The magnitude of these differences and the implications for understanding geological processes are investigated across a geologic contact between mare and highland in the Grimaldi Basin on the western nearside of the Moon. Vertical and lateral mass transport due to impact cratering has redistributed mare and highland materials across the contact, creating a gradient in composition. Solutions to linear and nonlinear spectral mixture models for identical spectral endmembers of mare, highland, and fresh crater materials are compared across this simple geologic contact in the Grimaldi Basin. Profiles of mare abundance across the contact are extracted and compared quantitatively. Profiles from the linear mixture models indicate that the geologic contact has an average mare abundance of 60%, and the compositional boundary is asymmetric with more mare transported onto the highland side of the contact than highland onto the mare side of the contact. In contrast the nonlinear abundance profiles indicate that the geologic contact has an average mare abundance of 50%, and the compositional boundary is remarkably symmetric. Given the expectation that materials will be intimately mixed on the surface of the Moon, and that the asymmetries implied by the linear model are not consistent with our understanding of lunar surface processes, the nonlinear spectral mixture model is preferred and should be applied whenever quantitative abundance information is required. The remarkable symmetry in the compositional gradients across this contact indicate that lateral mass transport dominates over vertical transport at this boundary.

Mustard, John F.↗