Salicylaldehyde based oxazolidines as catalysts for the asymmetric addition of diethylzinc to aldehydes

A series of oxazolidines have been prepared by condensation of N‐isopropyl norephedrine with a variety of salicylaldehyde derivatives. Despite the stereochemical relationship of (1R,2S)‐norephedrine with (1R,2S)‐ephedrine, the resultant oxazolidines 12‐14 were determined to have a stronger stereochemical relationship with (1S,2S)‐pseudoephedrine based oxazolidines. The resultant oxazolidines were used as catalytic ligands in the addition of diethylzinc to several aldehydes. It was determined that the oxazolidine derivative 12 gave the highest yield and a moderate enantioselectivity.     

High‐Affinity Proton Donors Promote Proton‐Coupled Electron Transfer by Samarium Diiodide

The relationship between proton‐donor affinity for Sm^II ions and the reduction of two substrates (anthracene and benzyl chloride) was examined. A combination of spectroscopic, thermochemical, and kinetic studies show that only those proton donors that coordinate or chelate strongly to Sm^II promote anthracene reduction through a PCET process. These studies demonstrate that the combination of Sm^II ions and water does not provide a unique reagent system for formal hydrogen atom transfer to substrates.     

Pictet–Spengler Synthesis of Quinoline‐Fused Porphyrins and Phenanthroline‐Fused Diporphyrins

Doubly and quadruply quinoline‐fused porphyrins were effectively synthesized through a reaction sequence consisting of Suzuki–Miyaura coupling of β‐borylated porphyrins with 2‐iodoaniline and subsequent Pictet–Spengler cyclization. These quinoline‐fused porphyrins display red‐shifted absorption bands and higher electron‐accepting abilities. This synthetic protocol also allowed the synthesis of phenanthroline‐fused porphyrin dimers, which bound either a Ni^II or Zn^II cation. The resultant metal complexes displayed further red shifted absorption spectra and molecular twists to effect an almost perpendicular arrangement of the two porphyrins.     

The Electrochemistry of Viologens with Various Alkyl Substituents and The Dimerization of Their 1e- Reduced Species in the Absence and Presence of Various Cyclodextrins

We present EQCM study for the electrochemical behavior of various 1-methyl-1'-alkylvilogen (C₁C_nV:n=1, 7-10, 12, 14,16, 18). In some viologens, we discussed the mechanism of CD-induced comproportionation reaction as well as electrodeposition pathway based on the EQCM and the spectroelectrochemical experimental results.     

A Learning Algorithm for the Control of Continuous Action Set-Point Regulator Systems

The convergence properties for reinforcement learning approaches, such as temporal differences and Q-learning, have been established under moderate assumptions for discrete state and action spaces. In practice, however, many systems have either continuous action spaces or a large number of discrete elements. This paper presents an approximate dynamic programming approach to reinforcement learning for continuous action set-point regulator problems, which learns near-optimal control policies based on scalar performance measures. The continuous-action space (CAS) algorithm uses derivative-free line search methods to obtain the optimal action in the continuous space. The theoretical convergence properties of the algorithm are presented. Several heuristic stopping criteria are investigated and practical application is illustrated by two example problems—the inverted pendulum balancing problem and the power system stabilization problem.     

A proposition on memes and meta-memes in computing for higher-order learning

In computational intelligence, the term ‘memetic algorithm’ has come to be associated with the algorithmic pairing of a global search method with a local search method. In a sociological context, a ‘meme’ has been loosely defined as a unit of cultural information, the social analog of genes for individuals. Both of these definitions are inadequate, as ‘memetic algorithm’ is too specific, and ultimately a misnomer, as much as a ‘meme’ is defined too generally to be of scientific use. In this paper, we extend the notion of memes from a computational viewpoint and explore the purpose, definitions, design guidelines and architecture for effective memetic computing. Utilizing two conceptual case studies, we illustrate the power of high-order meme-based learning. With applications ranging from cognitive science to machine learning, memetic computing has the potential to provide much-needed stimulation to the field of computational intelligence by providing a framework for higher order learning.     

Origin of Electric Field Dependence of the Charge Mobility and Spatial Energy Correlations in C60-Based Field Effect Transistors

We report on the influence of the lateral electric field on the charge mobility in organic field-effect transistors (OFET) based on C₆₀ films with multigrain morphology. The experimental data were quantitatively described using a recent analytical model by accounting for the strong local electric fields in a multigrain transistor channel and for the energy correlation effects. To rationalize the presence of a correlated disorder in a non-polar C₆₀ material, we show that randomly oriented permanent dipoles in organic gate dielectric layers can generate a significant dipolar disorder in an adjacent nonpolar semiconductor layer.     

Complex Classical Fields: A Framework for Reflection Positivity

We explore a framework for complex classical fields, appropriate for describing quantum field theories. Our fields are linear transformations on a Hilbert space, so they are more general than random variables for a probability measure. Our method generalizes Osterwalder and Schrader’s construction of Euclidean fields. We allow complex-valued classical fields in the case of quantum field theories that describe neutral particles. From an analytic point-of-view, the key to using our method is reflection positivity. We investigate conditions on the Fourier representation of the fields to ensure that reflection positivity holds. We also show how reflection positivity is preserved by various spacetime compactifications of ${\mathbb{R}^{d}}$ in different coordinate directions.     

Transients and Evolution in NiTi

Many of the applications that seek to utilize shape memory alloys for their unique set of properties inevitably must deal, on some level, with the dimensional instability that is inherent to these materials under cyclic thermomechanical loading conditions. As a result, a better understanding of the transient and evolutionary behavior of a shape memory alloy is critical to both the successful design of useful actuation systems and development of accurate material models that can adequately capture the types of dimensional instability that can arise during component design. To this end, a set of experiments were conducted wherein the temperature cycling excursion was held fixed while the applied stress was varied. The results indicated that the extent of strain evolution produced under the initially applied stress has a significant impact on both the amount of transient that is observed as well as the rate of evolution observed under subsequent stress levels. In particular, lowering the applied stress to 50 MPa after cycling under an initial stress of 75 MPa did not stabilize the strain. However, lowering the applied stress to 50 MPa after cycling under an initial stress of 150 MPa produced a nearly saturated strain/temperature response. The thermomechanical observations are discussed in terms of the nature of strain evolution and its connection to the concept of a local/global minimization of the energy of the system, however, the exact mechanisms associated with these strain evolutions were not determined.     

Probing the QCD critical point with relativistic heavy-ion collisions

We utilize an event-by-event relativistic hydrodynamic calculation performed at a number of different incident beam energies to investigate the creation of hot and dense QCD matter near the critical point. Using state-of-the-art analysis and visualization tools we demonstrate that each collision event probes QCD matter characterized by a wide range of temperatures and baryo-chemical potentials, making a dynamical response of the system to the vicinity of the critical point very difficult to isolate above the background.