Intramolecular proton transfer

[structure: see text] Reversal of the normal kinetic protonation stereochemistry results as a consequence of intramolecular delivery.     

Material frame representation of equivalent stress tensor for discrete solids

In this paper, we derive expressions for equivalent Cauchy and Piola stress tensors that can be applied to discrete solids and are exact for the case of homogeneous deformation. The main principles used for this derivation are material frame formulation, long wave approximation and decomposition of particle motion into continuum and thermal parts. Equivalent Cauchy and Piola stress tensors for discrete solids are expressed in terms of averaged interparticle distances and forces. No assumptions about interparticle forces are used in the derivation, thereby ensuring our expressions are valid irrespective of the choice of interatomic potential used to model the discrete solid. The derived expressions are used for calculation of the local Cauchy stress in several test problems. The results are compared with prediction of the classical continuum definition (force per unit area) as well as existing discrete formulations (Hardy, Lucy, and Heinz-Paul-Binder stress tensors). It is shown that in the case of homogeneous deformations and finite temperatures the proposed expression leads to the same values of stresses as classical continuum definition. Hardy and Lucy stress tensors give the same result only if the stress is averaged over a sufficiently large volume. Thus, given the lack of sensitivity to averaging volume size, the derived expressions can be used as benchmarks for calculation of stresses in discrete solids.     

Toward one‐pot olefin/thiophene block copolymers using an in situ ligand exchange

Block copolymers containing both conducting and insulating segments are of interest due to their enhanced electrical properties arising from their increased crystallization. Yet few methods exist for generating these copolymers, because the reaction conditions for synthesizing each block are often incompatible. Herein, efforts toward identifying a one‐pot, living polymerization method for synthesizing block copolymers of 1‐pentene and 3‐hexylthiophene is described. An in situ ligand exchange enables the optimal catalyst to be utilized for synthesizing each block. Even under these conditions, however, only homopolymers are observed. Computational studies modeling the ligand exchange reveal that the added stabilizing ligands likely inhibit propagation of the second block. These results suggest an ancillary ligand‐based “goldilocks” effect wherein catalysts that are stable yet still reactive are required. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1601–1605     

A two-step,single pot procedure for the synthesis of substituted dihydropyrazolo-pyrimidines

In this study, we report a two-step, one pot tandem microwave-assisted reaction of 3-formylchromones with aminopyrazoles followed by a tin-free radical addition. A library of alkyl substituted dihydropyrazolopyrimidines was prepared using this new process.     

The Torgegram for Fluvial Variography: Characterizing Spatial Dependence on Stream Networks

We introduce a graphical diagnostic called the Torgegram for characterizing spatial dependence among observations of a variable on a stream network. The Torgegram consists of four component empirical semivariograms, each one corresponding to a particular combination of flow-connectedness within the network and model type (tail-up/tail-down). We show how an overall strategy for fluvial variography can be based on a careful examination of the Torgegram. An analysis of water temperature data from a stream network within the Columbia River basin of the northwest United States illustrates the diagnostic value of the Torgegram as well as its limitations. Additional uses and extensions of the Torgegram are discussed.     

Heat transfer to air–water annular flow in a horizontal pipe

Two-phase air–water flow and heat transfer in a 25 mm internal diameter horizontal pipe were investigated experimentally. The water superficial velocity varied from 24.2 m/s to 41.5 m/s and the air superficial velocity varied from 0.02 m/s to 0.09 m/s. The aim of the study was to determine the heat transfer coefficient and its connection to flow pattern and liquid film thickness. The flow patterns were visualized using a high speed video camera, and the film thickness was measured by the conductive tomography technique. The heat transfer coefficient was calculated from the temperature measurements using the infrared thermography method. It was found that the heat transfer coefficient at the bottom of the pipe is up to three times higher than that at the top, and becomes more uniform around the pipe for higher air flow-rates. Correlations on local and average Nusselt number were obtained and compared to results reported in the literature. The behavior of local heat transfer coefficient was analyzed and the role of film thickness and flow pattern was clarified.     

“Beyond an acronym,STEM is…”: Perceptions of STEM

Although STEM is at the forefront of many educational initiatives, little is known about various professionals’ perceptions of STEM. This mixed‐methods study surveyed 164 preservice teachers, inservice teachers, administrators, informal educators, and STEM professionals. Quantitative and qualitative questions on the survey elicited participants’ perceptions of STEM, STEM support, and STEM careers. Quantitative analysis revealed that profession influenced understandings of STEM, importance of STEM, support for STEM, and perceptions of STEM career opportunities. Qualitative analysis provided rich explanations for the differences in perceptions among professions. This study suggests that science teacher educators need to ensure preservice teachers have understandings of STEM and STEM careers, K‐16 educators need to emphasize the current importance of STEM, and administrators and policymakers need to align visions of STEM with curriculum and pacing guides so teachers feel supported in their STEM endeavors.     

Locally conformal finite-difference time-domain techniques for particle-in-cell plasma simulation

The Dey–Mittra [S. Dey, R. Mitra, A locally conformal finite-difference time-domain (FDTD) algorithm for modeling three-dimensional perfectly conducting objects, IEEE Microwave Guided Wave Lett. 7 (273) 1997] finite-difference time-domain partial cell method enables the modeling of irregularly shaped conducting surfaces while retaining second-order accuracy. We present an algorithm to extend this method to include charged particle emission and absorption in particle-in-cell codes. Several examples are presented that illustrate the possible improvements that can be realized using the new algorithm for problems relevant to plasma simulation.     

Search for the rare decays K(L)→π0π0μ+μ- and K(L)→π0π0X0→π0π0μ+μ-

The KTeV E799 experiment has conducted a search for the rare decays, K(L)→π(0)π(0)μ(+)μ(-) and K(L)→π(0)π(0)X(0)→π(0)π(0)μ(+)μ(-), where the X(0) is a possible new neutral boson that was reported by the HyperCP experiment with a mass of (214.3 ± 0.5) MeV/c(2). We find no evidence for either decay. We obtain upper limits of Br(K(L)→π(0)π(0)X(0)→π(0)π(0)μ(+)μ(-)) < 1.0 × 10(-10) and Br(K(L)→π(0)π(0)μ(+)μ(-)) < 9.2 × 10(-11) at the 90% confidence level. This result rules out the pseudoscalar X(0) as an explanation of the HyperCP result under the scenario that the dsX(0) coupling is completely real.