Reductive Functionalization of a Rhodium(III)-Methyl Bond in Acidic Media: Key Step in the Electrophilic Oxidation of Methane
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We test the accuracy of Kohn–Sham density functional theory for strongly correlated metal–metal bonds that occur in catalytically active sites and intermediates and examine the orbitals and configurations involved to analyze the results.
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Correlated wavefunction theory predicts and high-resolution crystal structure analysis confirms the important, stabilizing effect of simultaneous hydrogen bond donor and acceptor interactions in proteins.
Herein we demonstrate a methodology for measuring optical pyrometry in environments which are disadvantageous for typical pyrometery applications by introducing additional fit parameters to account for absorption or emission which convolutes the thermal spectrum. Emission spectra from a plastic-bonded formulation of triaminotrinitrobenzene (TATB) shocked by 2-4 km s -1 impacts with Al flyer plates show significant deviations from graybody behavior. To extract reliable temperatures via optical pyrometry, we fit the spectra to a combination of a graybody and either a Gaussian absorption or emission spectrum. We found that the absorption needed to fit the data corresponds well with the known pressure-dependent absorption of TATB, and that the absorption model gives temperatures and emissivities in line with other explosives. By contrast, emission gives temperatures too low and emissivities that decrease as more material reacts. We conclude the nonthermal part of the spectrum is dominated by the absorption of unreacted TATB, and accurate pyrometry of TATB must use either our graybody plus absorption model or must limit the spectral range of observation to above 650 nm.
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Hf{sub 1−x−y}Al{sub x}Si{sub y}N (0 ≤ x ≤ 0.14, 0 ≤ y ≤ 0.12) single layer and multilayer films are grown on Si(001) at 250 °C using ultrahigh vacuum magnetically unbalanced reactive magnetron sputtering from a single Hf{sub 0.6}Al{sub 0.2}Si{sub 0.2} target in mixed 5%-N{sub 2}/Ar atmospheres at a total pressure of 20 mTorr (2.67 Pa). The composition and nanostructure of Hf{sub 1−x−y}Al{sub x}Si{sub y}N films are controlled by varying the energy E{sub i} of the ions incident at the film growth surface while maintaining the ion-to-metal flux ratio constant at eight. Switching E{sub i} between 10 and 40 eV allows the growth of Hf{sub 0.78}Al{sub 0.10}Si{sub 0.12}N/Hf{sub 0.78}Al{sub 0.14}Si{sub 0.08}N multilayers with similar layer compositions, but in which the Si bonding state changes from predominantly Si–Si/Si–Hf for films grown with E{sub i} = 10 eV, to primarily Si–N with E{sub i} = 40 eV. Multilayer hardness values, which vary inversely with bilayer period Λ, range from 20 GPa with Λ = 20 nm to 27 GPa with Λ = 2 nm, while fracture toughness increases directly with Λ. Multilayers with Λ = 10 nm combine relatively high hardness, H ∼ 24 GPa, with good fracture toughness.
Notch receptor activation initiates cell fate decisions and is distinctive in its reliance on mechanical force and protein glycosylation. The 2.5-angstrom-resolution crystal structure of the extracellular interacting region of Notch1 complexed with an engineered, high-affinity variant of Jagged1 (Jag1) reveals a binding interface that extends ~120 angstroms along five consecutive domains of each protein. O-Linked fucose modifications on Notch1 epidermal growth factor–like (EGF) domains 8 and 12 engage the EGF3 and C2 domains of Jag1, respectively, and different Notch1 domains are favored in binding to Jag1 than those that bind to the Delta-like 4 ligand. Jag1 undergoes conformational changes upon Notch binding, exhibiting catch bond behavior that prolongs interactions in the range of forces required for Notch activation. In conclusion, this mechanism enables cellular forces to regulate binding, discriminate among Notch ligands, and potentiate Notch signaling.
Bonding parameters and quality control for cadmium-stainless steel clad fuel pellet containment vessel production
Analysis of bonding and grounding measures for minimizing hazards from electrical fault, lightning, explosion, and electromagnetic radiation atKSC - Vol. 1
Preventive maintenance instructions for bonding and electrical grounding systems to prevent equipment damage by electrical faults, lightning, and radiation - Vol. 3
Development of adhesives for applications requiring long-term service at temperatures up to 600 F is discussed. This development work utilizes polyimide (PI) and polyphenylquinoxaline (PPQ) resin technology worked out previously. The resultant adhesives are evaluated in structural joints of titanium, steel and composite adherends and in honeycomb sandwich panels. Suitable adhesives also are evaluated in weld bonded titanium alloy joints. Testing includes determination of long-term aging of stressed and unstressed specimens at temperatures from about 450 F to 600 F as well as under dynamic fatigue conditions.
Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost, natural abundance of sodium. Here, we report a novel graphene nanosheets-wrapped phosphorus composite as an anode for high performance sodium-ion batteries though a facile ball-milling of red phosphorus and graphene nanosheets. Not only can the graphene nanosheets significantly improve the electrical conductivity, but they also serve as a buffer layer to accommodate the large volume change of phosphorus in the charge-discharge process. As a result, the graphene wrapped phosphorus composite anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and unique nanostructure can potentially extend to other electrode materials with unstable solid electrolyte interphases in sodium-ion batteries.
First Online: 21 June 2018 The authors would like to acknowledge the financial support given by the National Key Research and Development Program (Grant Number 2016YFB0300401), National Natural Science Foundation of China (Grant Number U1508215), Key Program of the Chinese Academy of Sciences (Grant Number ZDRW-CN-2017-1), and the National Natural Science Foundation of China (Grant Number 51774265). The authors would also like to thank Bijun Xie and Yifeng Guo for their help in the experimental work.
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Though hydrogen and lithium have been assigned a common column of the periodic table, their crystalline states under common conditions are drastically different: the former at temperatures where it is crystalline is a molecular insulator, whereas the latter is a metal that takes on simple structures. On compression, however, the two come to share some structural and other similarities associated with the insulator-to-metal and metal-to-insulator transitions, respectively. To gain a deeper understanding of differences and parallels in the behaviors of compressed hydrogen and lithium, we performed an ab initio comparative study of these systems in selected identical structures. Both elements undergo a continuous pressure-induced s-p electronic transition, though this is at a much earlier stage of development for H. The valence charge density accumulates in interstitial regions in Li but not in H in structures examined over the same range of compression. Moreover, the valence charge density distributions or electron localization functions for the same arrangement of atoms mirror each other as one proceeds from one element to the other. Application of the virial theorem shows that the kinetic and potential energies jump across the first-order phase transitions in H and Li are opposite in sign because of non-local effects in the Li pseudopotential. Finally, the common tendency of compressed H and Li to adopt three-fold coordinated structures as found is explained by the fact that such structures are capable of yielding a profound pseudogap in the electronic densities of states at the Fermi level, thereby reducing the kinetic energy. These results have implications for the phase diagrams of these elements and also for the search for new structures with novel properties.