2 resultados para Compra em Shopping Centers

em CaltechTHESIS


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With data centers being the supporting infrastructure for a wide range of IT services, their efficiency has become a big concern to operators, as well as to society, for both economic and environmental reasons. The goal of this thesis is to design energy-efficient algorithms that reduce energy cost while minimizing compromise to service. We focus on the algorithmic challenges at different levels of energy optimization across the data center stack. The algorithmic challenge at the device level is to improve the energy efficiency of a single computational device via techniques such as job scheduling and speed scaling. We analyze the common speed scaling algorithms in both the worst-case model and stochastic model to answer some fundamental issues in the design of speed scaling algorithms. The algorithmic challenge at the local data center level is to dynamically allocate resources (e.g., servers) and to dispatch the workload in a data center. We develop an online algorithm to make a data center more power-proportional by dynamically adapting the number of active servers. The algorithmic challenge at the global data center level is to dispatch the workload across multiple data centers, considering the geographical diversity of electricity price, availability of renewable energy, and network propagation delay. We propose algorithms to jointly optimize routing and provisioning in an online manner. Motivated by the above online decision problems, we move on to study a general class of online problem named "smoothed online convex optimization", which seeks to minimize the sum of a sequence of convex functions when "smooth" solutions are preferred. This model allows us to bridge different research communities and help us get a more fundamental understanding of general online decision problems.

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Notwithstanding advances in modern chemical methods, the selective installation of sterically encumbered carbon stereocenters, in particular all-carbon quaternary centers, remains an unsolved problem in organic chemistry. The prevalence of all-carbon quaternary centers in biologically active natural products and pharmaceutical compounds provides a strong impetus to address current limitations in the state of the art of their generation. This thesis presents four related projects, all of which share in the goal of constructing highly-congested carbon centers in a stereoselective manner, and in the use of transition-metal catalyzed alkylation as a means to address that goal.

The first research described is an extension of allylic alkylation methodology previously developed in the Stoltz group to small, strained rings. This research constitutes the first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones. Under Pd-catalysis, this chemistry affords all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.

Next is described our development of a (trimethylsilyl)ethyl β-ketoester class of enolate precursors, and their application in palladium–catalyzed asymmetric allylic alkylation to yield a variety of α-quaternary ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to allyl β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of our fluoride-triggered β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Lastly, our development of an Ir-catalyzed asymmetric allylic alkylation of cyclic β-ketoesters to afford highly congested, vicinal stereocenters comprised of tertiary and all-carbon quaternary centers with outstanding regio-, diastereo-, and enantiocontrol is detailed. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers. The chemistry is then extended to include acyclic β-ketoesters and similar levels of selective and functional group tolerance are observed. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands.