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41.
Antonio J. LaPorte Jack E. Feldner Jan C. Spies Tom J. Maher Prof. Martin D. Burke 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309566
Multifunctional organoboron compounds increasingly enable the simple generation of complex, Csp3-rich small molecules. The ability of boron-containing functional groups to modify the reactivity of α-radicals has also enabled a myriad of chemical reactions. Boronic esters with vacant p-orbitals have a significant stabilizing effect on α-radicals due to delocalization of spin density into the empty orbital. The effect of coordinatively saturated derivatives, such as N-methyliminodiacetic acid (MIDA) boronates and counterparts, remains less clear. Herein, we demonstrate that coordinatively saturated MIDA and TIDA boronates stabilize secondary alkyl α-radicals via σB-N hyperconjugation in a manner that allows site-selective C−H bromination. DFT calculated radical stabilization energies and spin density maps as well as LED NMR kinetic analysis of photochemical bromination rates of different boronic esters further these findings. This work clarifies that the α-radical stabilizing effect of boronic esters does not only proceed via delocalization of radical character into vacant boron p-orbitals, but that hyperconjugation of tetrahedral boron-containing functional groups and their ligand electron delocalizing ability also play a critical role. These findings establish boron ligands as a useful dial for tuning reactivity at the α-carbon. 相似文献
42.
Jorge A. Soria-Alcaraz Gabriela Ochoa Jerry Swan Martin Carpio Hector Puga Edmund K. Burke 《European Journal of Operational Research》2014
Course timetabling is an important and recurring administrative activity in most educational institutions. This article combines a general modeling methodology with effective learning hyper-heuristics to solve this problem. The proposed hyper-heuristics are based on an iterated local search procedure that autonomously combines a set of move operators. Two types of learning for operator selection are contrasted: a static (offline) approach, with a clear distinction between training and execution phases; and a dynamic approach that learns on the fly. The resulting algorithms are tested over the set of real-world instances collected by the first and second International Timetabling competitions. The dynamic scheme statistically outperforms the static counterpart, and produces competitive results when compared to the state-of-the-art, even producing a new best-known solution. Importantly, our study illustrates that algorithms with increased autonomy and generality can outperform human designed problem-specific algorithms. 相似文献
43.
Aleksandra Swiercz Edmund K. Burke Mateusz Cichenski Grzegorz Pawlak Sanja Petrovic Tomasz Zurkowski Jacek Blazewicz 《Central European Journal of Operations Research》2014,22(3):567-589
This paper introduces a new approach to applying hyper-heuristic algorithms to solve combinatorial problems with less effort, taking into account the modelling and algorithm construction process. We propose a unified encoding of a solution and a set of low level heuristics which are domain-independent and which change the solution itself. This approach enables us to address NP-hard problems and generate good approximate solutions in a reasonable time without a large amount of additional work required to tailor search methodologies for the problem in hand. In particular, we focused on solving DNA sequencing by hybrydization with errors, which is known to be strongly NP-hard. The approach was extensively tested by solving multiple instances of well-known combinatorial problems and compared with results generated by meta heuristics that have been tailored for specific problem domains. 相似文献
44.
S Ravizza J A D Atkin M H Maathuis E K Burke 《The Journal of the Operational Research Society》2013,64(9):1347-1360
With the expected continued increases in air transportation, the mitigation of the consequent delays and environmental effects is becoming more and more important, requiring increasingly sophisticated approaches for airside airport operations. Improved on-stand time predictions (for improved resource allocation at the stands) and take-off time predictions (for improved airport-airspace coordination) both require more accurate taxi time predictions, as do the increasingly sophisticated ground movement models which are being developed. Calibrating such models requires historic data showing how long aircraft will actually take to move around the airport, but recorded data usually includes significant delays due to contention between aircraft. This research was motivated by the need to both predict taxi times and to quantify and eliminate the effects of airport load from historic taxi time data, since delays and re-routing are usually explicitly considered in ground movement models. A prediction model is presented here that combines both airport layout and historic taxi time information within a multiple linear regression analysis, identifying the most relevant factors affecting the variability of taxi times for both arrivals and departures. The promising results for two different European hub airports are compared against previous results for US airports. 相似文献
45.
The proportional hazards regression model, when subjects enter the study in a staggered fashion, is studied. A strong martingale approach is used to model the two-time parameter counting processes. It is shown that well-known univariate results such as weak convergence and martingale inequalities can be extended to this two-dimensional model. Strong martingale theory is also used to prove weight convergence of a general weighted goodness-of-fit process and its weighted bootstrap counterpart. 相似文献
46.
In the last few years, a significant number of multi-objective metaheuristics have been proposed in the literature in order
to address real-world problems. Local search methods play a major role in many of these metaheuristic procedures. In this
paper, we adapt a recent and popular indicator-based selection method proposed by Zitzler and Künzli in 2004, in order to
define a population-based multi-objective local search. The proposed algorithm is designed in order to be easily adaptable,
parameter independent and to have a high convergence rate. In order to evaluate the capacity of our algorithm to reach these
goals, a large part of the paper is dedicated to experiments. Three combinatorial optimisation problems are tested: a flow
shop problem, a ring star problem and a nurse scheduling problem. The experiments show that our algorithm can be applied with
success to different types of multi-objective optimisation problems and that it outperforms some classical metaheuristics.
Furthermore, the parameter sensitivity analysis enables us to provide some useful guidelines about how to set the parameters. 相似文献
47.
Although they are simple techniques from the early days of timetabling research, graph colouring heuristics are still attracting significant research interest in the timetabling research community. These heuristics involve simple ordering strategies to first select and colour those vertices that are most likely to cause trouble if deferred until later. Most of this work used a single heuristic to measure the difficulty of a vertex. Relatively less attention has been paid to select an appropriate colour for the selected vertex. Some recent work has demonstrated the superiority of combining a number of different heuristics for vertex and colour selection. In this paper, we explore this direction and introduce a new strategy of using linear combinations of heuristics for weighted graphs which model the timetabling problems under consideration. The weights of the heuristic combinations define specific roles that each simple heuristic contributes to the process of ordering vertices. We include specific explanations for the design of our strategy and present the experimental results on a set of benchmark real world examination timetabling problem instances. New best results for several instances have been obtained using this method when compared with other constructive methods applied to this benchmark dataset. 相似文献
48.
49.
A pair 〈B,K〉 is a Namioka pair if K is compact and for any separately continuous , there is a dense A⊆B such that f is ( jointly) continuous on A×K. We give an example of a Choquet space B and separately continuous such that the restriction fΔ| to the diagonal does not have a dense set of continuity points. However, for K a compact fragmentable space we have: For any separately continuous and for any Baire subspace F of T×K, the set of points of continuity of is dense in F. We say that 〈B,K〉 is a weak-Namioka pair if K is compact and for any separately continuous and a closed subset F projecting irreducibly onto B, the set of points of continuity of fF| is dense in F. We show that T is a Baire space if the pair 〈T,K〉 is a weak-Namioka pair for every compact K. Under (CH) there is an example of a space B such that 〈B,K〉 is a Namioka pair for every compact K but there is a countably compact C and a separately continuous which has no dense set of continuity points; in fact, f does not even have the Baire property. 相似文献
50.
This paper concerns smoothing by infimal convolution for two large classes of functions: convex, proper and lower semicontinous as well as for (the nonconvex class of) convex-composite functions. The smooth approximations are constructed so that they epi-converge (to the underlying nonsmooth function) and fulfill a desirable property with respect to graph convergence of the gradient mappings to the subdifferential of the original function under reasonable assumptions. The close connection between epi-convergence of the smoothing functions and coercivity properties of the smoothing kernel is established. 相似文献