Publications

A series of novel C2-symmetric bisoxazoline ligands (benbox and benboxMe2) have been prepared. A variety of coordinatively unsaturated rhodium(III) complexes (3a−g, 4a−g) have been isolated. Trapping reactions of the agostically stabilized complex [RhCl2{(S,S)-ib-benbox(Me2)}] (4d) are described. Metal-to-aryl methyl migration reactions are described for the complex [RhMe{(S,S)-ip-benbox(Me2)}][BArf] (11c). Full characterization details and reactivity studies of air-stable, isolable, mononuclear, paramagnetic rhodium(II) complexes [RhCl2{(S,S)-tb-benbox(Me2)}(H)] (15e) and [RhCl2{dm-benbox(Me2)H}] (15g) are reported.

Abstract The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu 2 (μ,η 1 : η 1 ‐MeCN)][X] 2 (X=weakly coordinating anion, NTf 2 ( 1 a ), FAl[OC 6 F 10 (C 6 F 5 )] 3 ( 1 b ), Al[OC(CF 3 ) 3 ] 4 ( 1 c )) was replaced by white phosphorus (P 4 ) or yellow arsenic (As 4 ) to yield [(DPFN)Cu 2 (μ,η 2 : η 2 ‐E 4 )][X] 2 (E=P ( 2 a – c ), As ( 3 a – c )). The molecular structures in the solid state reveal novel coordination modes for E 4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E 4 tetrahedra. Reactions with N‐heterocyclic carbenes (NHCs) led to replacement of the E 4 tetrahedra with release of P 4 or As 4 and formation of [(DPFN)Cu 2 (μ,η 1 : η 1 ‐ Me NHC)][X] 2 ( 4 a,b ) or to an opening of one E−E bond leading to an unusual E 4 butterfly structural motif in [(DPFN)Cu 2 (μ,η 1 : η 1 ‐E 4 Dipp NHC)][X] 2 (E=P ( 5 a,b ), E=As ( 6 )). With a cyclic alkyl amino carbene ( Et CAAC), cleavage of two As−As bonds was observed to give two isomers of [(DPFN)Cu 2 (μ,η 2 : η 2 ‐As 4 Et CAAC)][X] 2 ( 7 a,b ) with an unusual As 4 ‐triangle+1 unit.

his paper studies under what conditions congestion control schemes can be both efficient, so that capacity is not wasted, and incentive compatible, so that each participant can maximize its utility by following the prescribed protocol. We show that both conditions can be achieved if routers run strict priority queueing (SPQ) or weighted fair queueing (WFQ) and end-hosts run any of a family of protocols which we call Probing Increase Educated Decrease (PIED). A natural question is whether incentive compatibility and efficiency are possible while avoiding the per-flow processing of WFQ. We partially address that question in the negative by showing that any policy satisfying a certain "locality" condition cannot guarantee both properties.

As established by the second law of thermodynamics, an isolated system is unable to exhibit complex behaviours. Conversely, a physical system, which interacts with the surrounding environment, may support emergent phenomena, provided some of its constitutive components are capable to amplify infinitesimal fluctuations in energy under suitable polarization, a property which is referred to as Local Activity. Local Activity is in fact a New Universal Physics Principle, which, grounded on solid theoretical foundations, enables to explain emergent phenomena in any open system, e.g., the emergence of the All-to-None phenomenon in neurons, and Symmetry-Breaking Effects in biological homogeneous cellular media. The existence of solid-state memristor nano-devices, which, similarly as the sodium and potassium ion channels, may operate in the Local Activity domain under opportune bias conditions, opens up new opportunities to synthesise circuits and systems, which, operating according to biological principles, may outperform traditional computing structures in terms of time and energy efficiency. This tutorial aims to shed light on the precious role that Nonlinear Circuit and System Theory shall assume in the years to come to support the exploration of the full potential of memristor physical realizations, which clearly show signs of Local Activity while admitting a Negative Differential Resistance upon suitable DC excitation, for bio-inspired electronics.

The synthesis of gold nanorods remains largely heuristically understood. Large language models provide a route for extracting their structured synthesis procedures from scientific articles to accelerate investigation into synthesis pathways.

Abstract For Abstract see ChemInform Abstract in Full Text.

By introducing memristors into circuit design, the limitations of traditional purely-CMOS hardware may be overcome. However, an extension of standard techniques for the analysis and design of conventional computing structures may be necessary to allow their applicability to the memristive counterparts. This paper adopts a generalization of the Dynamic Route Map system-theoretic concept to elucidate the mechanisms by which bio-inspired arrays of locally-coupled circuits, employing memristors with either bistable-like or analogue dynamic switching behaviours, accomplish image mem-processing tasks through the dynamical evolution of their states toward predefined equilibria.

Understanding how living cells interact with nanostructures is integral to a better understanding of the fundamental principles of biology and the development of next-generation biomedical/bioenergy devices. Recent studies have demonstrated that mammalian cells can recognize nanoscale topographies and respond to these structures. From this perspective, there is a growing recognition that nanostructures, along with their specific physicochemical properties, can also be used to regulate the responses and motions of bacterial cells. Here, by utilizing a well-defined silicon nanowire array platform and single-cell imaging, we present direct evidence that Shewanella oneidensis MR-1 can recognize nanoscale structures and that their swimming patterns and initial attachment locations are strongly influenced by the presence of nanowires on a surface. Analyses of bacterial trajectories revealed that MR-1 cells exhibited a confined diffusion mode in the presence of nanowires and showed preferential attachment to the nanowires, whereas a superdiffusion mode was observed in the absence of nanowires. These results demonstrate that nanoscale topography can affect bacterial movement and attachment and play an important role during the early stages of biofilm formation.