Isomerization of Secondary Phosphirane into Terminal Phosphinidene Complexes: An Analogy between Monovalent Phosphorus and Transition Metals

Secondary phosphirane complexes isomerize above 100 °C to give the corresponding terminal phosphinidene complexes, which can be trapped by alkenes and alkynes. This reaction is a rare instance of the isomerization of a P^III derivative into a P^I derivative. It appears to mimic the reductive elimination of alkanes from transition‐alkylmetal hydrides.     

Novel total synthesis of anserinone A and B

Anserinones A and B are natural products that have been shown to have potential anticancer, antifungal, and antibacterial properties. This work entails the novel synthesis of these natural products.     

On separating a fixed point from zero by invariants

Assume a fixed point v∈V^G can be separated from zero by a homogeneous invariant f∈𝕜[V]^G of degree p^rd, where p>0 is the characteristic of the ground field 𝕜 and p,d are coprime. We show that then v can also be separated from zero by an invariant of degree p^r, which we obtain explicitly from f. It follows that the minimal degree of a homogeneous invariant separating v from zero is a p-power.     

Geometric modeling and analysis of detonation cellular stability

A geometric model with a low computational complexity capable of simulating detonation behavior in physical systems is proposed. In support of the geometric model development, a series of cylindrical 1D simulations with a variable size initiation kernel are performed in hydrogen-oxygen mixtures. From these 1D simulations a detonation cell stabilization mechanism is identified. The stabilization mechanism is predicated on the size of the gap between the pressure and temperature fronts at the point where the average pressure front velocity along one cell length is equal to the CJ velocity. This gap, in a multidimensional detonation, is the ignition kernel of a subsequent blast, and dictates the formation of the subsequent cell. Serial analysis of blasts in this context leads to a unique stable blast kernel size for any mixture, which, within the uncertainty of the initial kernel state, can predict the experimental cell length for mixtures considered in this study. Using a tabulation of the 1D simulations as an input, a formulation and sample results of the geometric model are shown. The geometric model can reproduce both qualitative and quantitative features of experimental detonation cellular structure.     

The Consensus Problem in Polities of Agents with Dissimilar Cognitive Architectures

Agents interacting with their environments, machine or otherwise, arrive at decisions based on their incomplete access to data and their particular cognitive architecture, including data sampling frequency and memory storage limitations. In particular, the same data streams, sampled and stored differently, may cause agents to arrive at different conclusions and to take different actions. This phenomenon has a drastic impact on polities—populations of agents predicated on the sharing of information. We show that, even under ideal conditions, polities consisting of epistemic agents with heterogeneous cognitive architectures might not achieve consensus concerning what conclusions to draw from datastreams. Transfer entropy applied to a toy model of a polity is analyzed to showcase this effect when the dynamics of the environment is known. As an illustration where the dynamics is not known, we examine empirical data streams relevant to climate and show the consensus problem manifest.     

Correlating conductivity and Seebeck coefficient to doping within crystalline and amorphous domains in poly(3-(methoxyethoxyethoxy)thiophene)

Molecular doping of conjugated polymers (CPs) plays a vital role in optimizing organic electronic and energy applications. For the case of organic thermoelectrics, it is commonly believed that doping CPs with a strong dopant could result in higher conductivity (σ) and thus better power factor (PF). Herein, by investigating thermoelectric performance of a polar side-chain bearing CP, poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET), vapor doped with fluorinated-derivative of tetracyanoquinodimethane FnTCNQ (n = 1, 2, 4), we show that using strong dopants can in fact have detrimental effects on the thermoelectric performance of CPs. Despite possessing higher electron affinity, doping P3MEET with F4TCNQ only results in a σ (27.0 S/cm) comparable to samples doped with other two weaker dopants F2TCNQ and F1TCNQ (26.4 and 20.1 S/cm). Interestingly, F4TCNQ-doped samples display a marked reduction in the Seebeck coefficient (α) compared to F1TCNQ- and F2TCNQ-doped samples from 42 to 13 μV/K, leading to an undesirable suppression of the PF. Structural characterizations coupled with Kang-Snyder modeling of the α–σ relation show that the reduction of α in F4TCNQ-doped P3MEET samples originates from the generation of low mobility carrier within P3MEET's amorphous domain. Our results demonstrate that factors such as dopant distribution and doping efficiency within the crystalline and amorphous domains of CPs should play a crucial role in advancing rational design for organic thermoelectrics.     

Untersuchung von Bier, Bierroh- und Zwischenerzeugnissen

Ohne Zusammenfassung