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.     

Isolation and On‐Line LC/CD Analysis of 3,8″‐Linked Biflavonoids from Gnidia involucrata

Investigation of the methanol extract of the roots of Gnidia involucrata (Thymelaeaceae) led to the isolation and characterization of two new 3,8″‐biflavonoid diastereoisomers, named GB‐4 ( 6a ) and GB‐4a ( 6b ). Their absolute configurations were determined in mixture by on‐line LC/CD measurements, which also allowed the revision of absolute configurations of the biflavanoids GB‐1 and GB‐2, and the configurational assignment of GB‐3.     

RANDOM EDGE can be exponential on abstract cubes

We prove that RANDOM EDGE, the simplex algorithm that always chooses a random improving edge to proceed on, can take a mildly exponential number of steps in the model of abstract objective functions (introduced by Williamson Hoke [Completely unimodal numberings of a simple polytope, Discrete Appl. Math. 20 (1988) 69-81.] and by Kalai [A simple way to tell a simple polytope from its graph, J. Combin. Theory Ser. A 49(2) (1988) 381-383.] under different names). We define an abstract objective function on the n-dimensional cube for which the algorithm, started at a random vertex, needs at least exp(const·n^1/3) steps with high probability. The best previous lower bound was quadratic. So in order for RANDOM EDGE to succeed in polynomial time, geometry must help.     

A Verified Optimization Technique to Locate Chaotic Regions of Hénon Systems

We present a new verified optimization method to find regions for Hénon systems where the conditions of chaotic behaviour hold. The present paper provides a methodology to verify chaos for certain mappings and regions. We discuss first how to check the set theoretical conditions of a respective theorem in a reliable way by computer programs. Then we introduce optimization problems that provide a model to locate chaotic regions. We prove the correctness of the underlying checking algorithms and the optimization model. We have verified an earlier published chaotic region, and we also give new chaotic places located by the new technique.