A control-theoretic perspective on optimal high-order optimization

Mathematical Programming - We provide a control-theoretic perspective on optimal tensor algorithms for minimizing a convex function in a finite-dimensional Euclidean space. Given a function...     

Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Compatible relations on filters and stability of local topological properties under supremum and product

An abstract scheme using particular types of relations on filters leads to general unifying results on stability under supremum and product of local topological properties. We present applications for Fréchetness, strong Fréchetness, countable tightness and countable fan-tightness, some of which recover or refine classical results, some of which are new. The reader may find other applications as well.     

Globally Linked Pairs of Vertices in Equivalent Realizations of Graphs

A two-dimensional framework (G,p) is a graph G = (V,E) together with a map p: V → ℝ². We view (G,p) as a straight line realization of G in ℝ². Two realizations of G are equivalent if the corresponding edges in the two frameworks have the same length. A pair of vertices {u,v} is globally linked in G if %and for all equivalent frameworks (G,q), the distance between the points corresponding to u and v is the same in all pairs of equivalent generic realizations of G. The graph G is globally rigid if all of its pairs of vertices are globally linked. We extend the characterization of globally rigid graphs given by the first two authors [13] by characterizing globally linked pairs in M-connected graphs, an important family of rigid graphs. As a byproduct we simplify the proof of a result of Connelly [6] which is a key step in the characterization of globally rigid graphs. We also determine the number of distinct realizations of an M-connected graph, each of which is equivalent to a given generic realization. Bounds on this number for minimally rigid graphs were obtained by Borcea and Streinu in [3].     

Constructing orthogonal pandiagonal Latin squares and panmagic squares from modular n‐queens solutions

In this article, we show how to construct pairs of orthogonal pandiagonal Latin squares and panmagic squares from certain types of modular n‐queens solutions. We prove that when these modular n‐queens solutions are symmetric, the panmagic squares thus constructed will be associative, where for an n × n associative magic square A = (a_ij), for all i and j it holds that a_ij + an?i?1,n?j?1 = c for a fixed c. We further show how to construct orthogonal Latin squares whose modular difference diagonals are Latin from any modular n‐queens solution. As well, we analyze constructing orthogonal pandiagonal Latin squares from particular classes of non‐linear modular n‐queens solutions. These pandiagonal Latin squares are not row cyclic, giving a partial solution to a problem of Hedayat. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 221–234, 2007