Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites

Replacing the Pb−X octahedral building unit of A^IPbX₃ perovskites (X=halide) with a pair of edge-sharing Pb−X octahedra affords the expanded perovskite analogs: A^IIPb₂X₆. We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with A^II=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of A^IIPb₂X₆. The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.     

The cultural Red King effect

Why do minority groups tend to be discriminated against when it comes to situations of bargaining and resource division? In this article, I explore an explanation for this disadvantage that appeals solely to the dynamics of social interaction between minority and majority groups—the cultural Red King effect (Bruner, 2017). As I show, in agent-based models of bargaining between groups, the minority group will tend to get less as a direct result of the fact that they frequently interact with majority group members, while majority group members meet them only rarely. This effect is strengthened by certain psychological phenomenon—risk aversion and in-group preference—is robust on network models, and is strengthened in cases where preexisting norms are discriminatory. I will also discuss how this effect unifies previous results on the impacts of institutional memory on bargaining between groups.     

Diffraction enhanced imaging of soft tissues

The APS hosted a two-day workshop on Catalysis Research at the APS on September 12-13, 2005. The goal of the workshop was to evaluate current catalysis-related research at the APS and to plan future directions. The outcome of the meeting will be a report with recommendations to promote new, and support current, catalysis research at the APS. The workshop was attended by 82 participants representing industry, national laboratories, and universities.     

Catalytic Enantioselective Direct Aldol Addition of Aryl Ketones to α‐Fluorinated Ketones

The catalytic enantioselective synthesis of α‐fluorinated chiral tertiary alcohols from (hetero)aryl methyl ketones is described. The use of a bifunctional iminophosphorane (BIMP) superbase was found to facilitate direct aldol addition by providing the strong Brønsted basicity required for rapid aryl enolate formation. The new synthetic protocol is easy to perform and tolerates a broad range of functionalities and heterocycles with high enantioselectivity (up to >99:1 e.r.). Multi‐gram scalability has been demonstrated along with catalyst recovery and recycling. ¹H NMR studies identified a 1400‐fold rate enhancement under BIMP catalysis, compared to the prior state‐of‐the‐art catalytic system. The utility of the aldol products has been highlighted with the synthesis of various enantioenriched building blocks and heterocycles, including 1,3‐aminoalcohol, 1,3‐diol, oxetane, and isoxazoline derivatives.     

Associations between Neurocardiovascular Signal Entropy and Physical Frailty

In this cross-sectional study, the relationship between noninvasively measured neurocardiovascular signal entropy and physical frailty was explored in a sample of community-dwelling older adults from The Irish Longitudinal Study on Ageing (TILDA). The hypothesis under investigation was that dysfunction in the neurovascular and cardiovascular systems, as quantified by short-length signal complexity during a lying-to-stand test (active stand), could provide a marker for frailty. Frailty status (i.e., “non-frail”, “pre-frail”, and “frail”) was based on Fried’s criteria (i.e., exhaustion, unexplained weight loss, weakness, slowness, and low physical activity). Approximate entropy (ApEn) and sample entropy (SampEn) were calculated during resting (lying down), active standing, and recovery phases. There was continuously measured blood pressure/heart rate data from 2645 individuals (53.0% female) and frontal lobe tissue oxygenation data from 2225 participants (52.3% female); both samples had a mean (SD) age of 64.3 (7.7) years. Results revealed statistically significant associations between neurocardiovascular signal entropy and frailty status. Entropy differences between non-frail and pre-frail/frail were greater during resting state compared with standing and recovery phases. Compared with ApEn, SampEn seemed to have better discriminating power between non-frail and pre-frail/frail individuals. The quantification of entropy in short length neurocardiovascular signals could provide a clinically useful marker of the multiple physiological dysregulations that underlie physical frailty.     

Effects of superglue fuming on materials characterization of zip-lock polyethylene bags for route forensic analyses

Using cyanoacrylate or “superglue” fuming to develop latent dermatoglyphic prints significantly altered the volatile and semivolatile compounds within the material of polyethylene zip-lock bags. Comparisons of SPME-GC/MS analyses of poly bags obtained before and after application of a glue fuming fingermark-developing technique resulted in markedly different material profiles of the bags. Not only were species added to the chemical composition of a bag, but other compounds that had been initially present were removed. These effects are particularly important for nuclear forensic investigations in the realm of route (pathway) analyses, and may also be of general interest to criminalistics laboratories that examine illicit drugs and their packaging.     

Selective formation of non-conjugated olefins by samarium(II)-mediated elimination/isomerization of allylic benzoates

Aromatic allylic benzoates can be selectively transformed to the corresponding benzoate eliminated olefin by the action of samarium diiodide. Depending on the substrate and the elimination conditions, high selectivity for the non-conjugated alkene product can be achieved.