Cyclol derivatives related to ergocornine

Novel cyclol derivatives (Table 1, 15, 16 ) similar in structure to the peptide portion of ergocornine were synthesized. Detailed experimental procedures are given for the preparation of the cis- 13a and the unknown trans- 14a cyclol esters.     

Quantitative atomic-scale analysis of interface structures: transmission electron microscopy and local density functional theory

Transmission electron microscopy (TEM) and local density functional theory (LDFT) are combined to analyze the microscopic structure of the rhombohedral twin interface in alpha-Al2O3. LDFT provides interfacial energetics and atomic and electronic structures for three competing models. With high-resolution TEM the atomic structure at the interface is imaged quantitatively along two orthogonal zone axes. Electron energy loss spectroscopy in TEM with nanoscale spatial resolution yields the interfacial electronic structure. Both experiments confirm the theoretically preferred model quantitatively.     

Weighted Sobolev spaces with applications to singular nonlinear boundary value problems

Variational methods are used in a weighted Sobolev space to prove the existence of solutions for a certain class of singular nonlinear ordinary differential equations.     

Dominance of the final state in photoemission mapping of the fermi surface of Co/Cu(001)

The Fermi surface of tetragonally distorted fcc Co films grown on Cu(001) has been investigated with first-principles calculations and compared with an experimental determination using angle-resolved photoemission. The angular distributions for hnu=21-45 eV are dominated by the structure of the final states rather than by the shape of the Fermi surface. Theoretical estimates of the photoemission matrix elements support this observation. This suggests that photoemission can have limitations in mapping Fermi surfaces, especially for materials that exhibit flat, closely spaced valence bands.     

An abstract averaging theorem

For each t ? 0, let A(t) generate a contraction semigroup on a Banach space L. Suppose the solution of u_t = ?A(t)u is given by an evolution operator V_?(t, s). Conditions are given under which $\text{V}{}_{\mathrm{?}}\text{(}\text{(t+s)}\text{?}\text{,}\text{s}\text{?}\text{)}$ converges strongly as ? → 0 to a semigroup T(t) generated by the closure of $\text{A}\text{?}\text{f ≡}\text{lim}{}_{\mathrm{T\to \infty }}\text{(}\text{1}\text{T}\text{) ∝}{}_0{}^{\mathrm{T}}\text{A(t)f dt}$.This result is applied to the following situation: Let B generate a contraction group S(t) and the closure of ?A + B generate a contraction semigroup S_?(t). Conditions are given under which $\text{S(?}\text{t}\text{?}\text{) S}{}_{\mathrm{?}}\text{(}\text{t}\text{?}\text{)}$ converges strongly to a semigroup generated by the closure of $\text{A}\text{?}\text{f ≡}\text{lim}{}_{\mathrm{T\to \infty }}\text{(}\text{1}\text{T}\text{) ∝ S(?t) AS(t)f dt}$. This work was motivated by and generalizes a result of Pinsky and Ellis for the linearized Boltzmann Equation.     

Dislocation vs. production bias revisited with account of radiation-induced emission bias. I. Void swelling under electron and light ion irradiation

Early experimental data on void swelling in electron-irradiated materials disagree with the dislocation bias models based on the dislocation-point defect elastic interactions. Later, this became one of the factors that prompted the development of models based on production bias (PBM) as the main driver for swelling, which assumed that the dislocation bias was much lower than that predicted by theoretical analyses of dislocation bias. However, the PBM in its present form fails to account for important and common observations, namely, the indefinite void growth often observed under cascade irradiation and the swelling saturation observed under high-dose irradiation and in void lattices. In this paper, we show that these contradictions can be naturally resolved in the framework of the rate theory that accounts for the radiation-induced vacancy emission from extended defects, such as voids, dislocations and grain boundaries. This modification introduces a new bias type in the theory, namely, the emission bias. This modified rate theory agrees well with the experimental data and demonstrates that the original dislocation bias should be used in rate theory models along with the emission bias in different irradiation environments. The modified theory predictions include, but are not limited to, the radiation-induced annealing of voids, swelling saturation under high-dose irradiation, generally, and in void lattices, in particular.     

"Click"-capture, ring-opening metathesis polymerization (ROMP), release: facile triazolation utilizing ROMP-derived oligomeric phosphates

Soluble, high-load ring-opening metathesis polymerization (ROMP)-derived oligomeric triazole phosphates (OTP) are reported for application as efficient triazolating reagents of nucleophilic species. Utilizing a "Click"-capture, ROMP, release protocol, the efficient and purification-free, direct triazolation of N-, O-, and S-nucleophilic species was successfully achieved. A variety of OTP derivatives were rapidly synthesized as free-flowing solids on a multigram scale from commercially available materials.     

Monomer-on-monomer (MoM) Mitsunobu reaction: facile purification utilizing surface-initiated sequestration

A monomer-on-monomer (MoM) Mitsunobu reaction utilizing norbornenyl-tagged (Nb-tagged) reagents is reported, whereby purification was rapidly achieved by employing ring-opening metathesis polymerization, which was initiated by any of three methods utilizing Grubbs catalyst: (i) free catalyst in solution, (ii) surface-initiated catalyst-armed silica, or (iii) surface-initiated catalyst-armed Co/C magnetic nanoparticles.     

Strong Metal–Support Interactions between Copper and Iron Oxide during the High‐Temperature Water‐Gas Shift Reaction

The commercial high‐temperature water‐gas shift (HT‐WGS) catalyst consists of CuO‐Cr₂O₃‐Fe₂O₃, where Cu functions as a chemical promoter to increase the catalytic activity, but its promotion mechanism is poorly understood. In this work, a series of iron‐based model catalysts were investigated with in situ or pseudo in situ characterization, steady‐state WGS reaction, and density function theory (DFT) calculations. For the first time, a strong metal‐support interaction (SMSI) between Cu and FeO_x was directly observed. During the WGS reaction, a thin FeO_x overlayer migrates onto the metallic Cu particles, creating a hybrid surface structure with Cu‐FeO_x interfaces. The synergistic interaction between Cu and FeO_x not only stabilizes the Cu clusters, but also provides new catalytic active sites that facilitate CO adsorption, H₂O dissociation, and WGS reaction. These new fundamental insights can potentially guide the rational design of improved iron‐based HT‐WGS catalysts.