A Short and Efficient Synthesis of the [3]Triangulene Ring System

Triangulenes are of current interest for potential applications in molecular electronics. We describe here a three step synthesis of the 4,8,12‐trihydro[3]triangulenium cation by cascade cyclization of a tetra‐benzyl alcohol precursor in triflic acid solution. This stable carbocation is easily observed by NMR and optical spectroscopy and is highly fluorescent. Quenching of the cation into basic solutions or by hydride transfer from triethylsilane provides access to stable dihydro and tetrahydro[3]triangulenes. These neutral species interconvert with cations in a complex series of proton and hydride transfers. This route provides several important [3]triangulene precursors. Preliminary experiments designed to generate [3]triangulene in the solution phase provide evidence for its formation and rapid oligomerization.     

Cycloelimination of Imidazolidin‐2‐ylidene N‐Heterocyclic Carbenes: Mechanism and Insights into the Synthesis of Stable “NHC‐CDI” Amidinates

We report the discovery that 1,3‐bis(aryl)imidazolidin‐2‐ylidenes, one of the most widely studied classes of N‐heterocyclic carbenes (NHCs), undergo quantitative conversion to zwitterionic “NHC‐CDI” amidinates upon heating to ≈100 °C in solution. The mechanism of this novel NHC decomposition process is studied in detail. These studies enabled the rational synthesis of a new class of bench stable amidinates from a panel of NHCs and carbodiimides. We expect these constructs to find utility in a variety of applications.     

Effect of monovalent ion binding on molecular dynamics of the S100-family calcium-binding protein calbindin D9k

Calbindin D_9k is a member of the S100 subfamily of EF-hand calcium binding proteins, and has served as an important model system for biophysical studies. The fast timescale dynamics of the calcium-free (apo) state is characterized using molecular dynamics simulations. Order parameters for the backbone NH bond vectors are determined from the simulations and compared with experimentally derived values, with a focus on the dynamics of calcium-binding site I. There is a significant discrepancy between simulated and experimental order parameters for site I residues in the case of no ion bound in site I. However, it was found in the simulations that a Na⁺ ion can bind in site I, and the resulting order parameters determined from the simulations are in excellent agreement with experiment. Comparisons are made to X-ray structures of other S100 family members in which Na⁺ ions were observed or suggested to be bound in site I. © 2019 Wiley Periodicals, Inc.     

Embedding Banach spaces into the space of bounded functions with countable support

We prove that a WLD subspace of the space consisting of all bounded, countably supported functions on a set Γ embeds isomorphically into if and only if it does not contain isometric copies of . Moreover, a subspace of is constructed that has an unconditional basis, does not embed into , and whose every weakly compact subset is separable (in particular, it cannot contain any isomorphic copies of ).     

Aircraft selection modeling: a multi-step heuristic to enumerate airlift alternatives

Annals of Operations Research - We consider the use of the new C-130J-30 aircraft for long distance (strategic) cargo movement. Currently, only large aircraft, the C-5 and the C-17, are identified...