Packing and covering the plane with translates of a convex polygon

A covering of the Euclidean plane by a polygon P is a system of translated copies of P whose union is the plane, and a packing of P in the plane is a system of translated copies of P whose interiors are disjoint. A lattice covering is a covering in which the translates are defined by the points of a lattice, and a lattice packing is defined similarly. We show that, given a convex polygon P with n vertices, the densest lattice packing of P in the plane can be found in O(n) time. We also show that the sparsest lattice covering of the plane by a centrally symmetric convex polygon can be solved in O(n) time. Our approach utilizes results from classical geometry that reduce these packing and covering problems to the problems of finding certain extremal enclosed figures within the polygon.     

Generalized Greatest Common Divisors,Divisibility Sequences,and Vojta’s Conjecture for Blowups

We apply Vojta’s conjecture to blowups and deduce a number of deep statements regarding (generalized) greatest common divisors on varieties, in particular on projective space and on abelian varieties. Special cases of these statements generalize earlier results and conjectures. We also discuss the relationship between generalized greatest common divisors and the divisibility sequences attached to algebraic groups, and we apply Vojta’s conjecture to obtain a strong bound on the divisibility sequences attached to abelian varieties of dimension at least two.     

Development of an asymmetric trimethylenemethane cycloaddition reaction: application in the enantioselective synthesis of highly substituted carbocycles

A protocol for the enantioselective [3+2] cycloaddition of trimethylenemethane (TMM) with electron-deficient olefins has been developed. The synthesis of novel phosphoramidite ligands was critical in this effort, and the preparation and reactivity of these ligands is detailed. The evolution of the ligand design, commencing with acyclic amine-derived phosphoramidites and leading to cyclic pyrrolidine and azetidine structures, is discussed. The conditions developed to effect an asymmetric TMM reaction using 2-trimethylsilylmethyl allyl acetate were shown to be tolerant of a wide variety of alkene acceptors, providing the desired methylenecyclopentanes with high levels of enantioselectivity. The donor scope was also explored, and substituted systems were tolerated, including one bearing a nitrile moiety. These donors were reactive with unsaturated acylpyrroles, giving the product cyclopentane rings bearing three stereocenters in high enantioselectivity and complete diastereoselectivity.     

Chemical rescue of enzymes: proton transfer in mutants of human carbonic anhydrase II

In human carbonic anhydrase II (HCA II), the mutation of position 64 from histidine to alanine (H64A) disrupts the rate limiting proton transfer (PT) event, resulting in a reduction of the catalytic activity of the enzyme as compared to the wild-type. Potential of mean force (PMF) calculations utilizing the multistate empirical valence bond (MS-EVB) methodology for H64A HCA II yields a PT free energy barrier significantly higher than that found in the wild-type enzyme. This high barrier, determined in the absence of exogenous buffer and assuming no additional ionizable residues in the PT pathway, indicates the likelihood of alternate enzyme pathways that utilize either ionizable enzyme residues (self-rescue) and/or exogenous buffers (chemical rescue). It has been shown experimentally that the catalytic activity of H64A HCA II can be chemically rescued to near wild-type levels by the addition of the exogenous buffer 4-methylimidazole (4MI). Crystallographic studies have identified two 4MI binding sites, yet site-specific mutations intended to disrupt 4MI binding have demonstrated these sites to be nonproductive. In the present work, MS-EVB simulations show that binding of 4MI near Thr199 in the H64A HCA II mutant, a binding site determined by NMR spectroscopy, results in a viable chemical rescue pathway. Additional viable rescue pathways are also identified where 4MI acts as a proton transport intermediary from the active site to ionizable residues on the rim of the active site, revealing a probable mode of action for the chemical rescue pathway.     

Coefficient inequalities for a subclass of starlike functions

A function f(z) = z ? ∑^∞_{n = 2}a_nzⁿ, a_n ? 0, analytic and univalent in the unit disk, is said to be in the family $\text{T}{}^1\text{(a, b)}$, a real and b ? 0, if $\text{¦(}\text{zf′}\text{f}\text{) ? a¦ ? b}$ for all z in the unit disk. A complete characterization is found for $\text{T}{}^1\text{(a, b)}$ when a ? 1. Also, sharp coefficient bounds are determined for certain subclasses of $\text{T}{}^1\text{(a, b)}$ when a < 1; however, examples are given to show that these bounds do not remain valid for the whole family.