Is the US stock market becoming weakly efficient over time? Evidence from 80-year-long data

We propose a degree of market efficiency in terms of entropy concepts. The relative efficiency for the US stock market varies over time from 1929 to 2012, with a slight decline in the past 10 years.     

Metal Oxide Assisted Preparation of Core–Shell Beads with Dense Metal–Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants

Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L^?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings.     

Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis

The triflimide iron(III) salt [Fe(NTf₂)₃] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the Fe^III cation mediated by the weakly‐coordinating triflimide anion is crucial for the catalytic activity. The iron(III) metal salt can be recycled in the form of the OPPh₃/[Fe(NTf₂)₃] system with similar activity and selectivity. However, spectroscopic and kinetic studies show that [Fe(NTf₂)₃] hydrolyzes under the reaction conditions and that catalytically less active Brønsted species are formed, which points to a Lewis/Brønsted co‐catalysis. This triflimide‐based catalytic system is regioselective for the hydration of internal aryl‐alkynes and opens the door to a new synthetic route to alkyl ketophenones. As a proof of concept, the synthesis of two antipsychotics Haloperidol and Melperone, with general butyrophenone‐like structure, is shown.     

Long‐Term Structural Evolution of an Intercalated Layered Semiconductor

Intercalated molecules can dramatically modify the electronic band structure of layered semiconductors, significantly altering the optical properties of the material. In the layered monochalcogenide Gallium Telluride (GaTe), exposure to air induces a nearly 1 eV reduction of its band gap due to the interlayer diffusion and chemisorption of oxygen. The effect of oxygen chemisorption at the Te‐terminated surfaces on the structure of GaTe, however, is much less known. To better understand the structure–property relationship of intercalated GaTe, a systematic, long‐term, X‐ray diffraction study has been performed on GaTe exfoliated crystals exposed to ambient conditions. It is observed that the structural changes are not limited to a previously observed short‐term increase in lattice expansion. Over the course of months and even years after exfoliation, the oxygen adsorbates continue to modify the structure of GaTe, inducing significant disorder and grain reorientation. It is estimated that approximately one out of every two grains is slightly displaced by the intercalating oxygen, demonstrating a significant increase in grain mosaicity, while still maintaining the original {?2 0 1} out‐of‐plane texture. Correlating these structural transformations to observed changes in electrical and optical properties will enable capitalization of the use of adsorbates to engineer novel properties in these layered materials.     

Disjoining pressure and the film-height-dependent surface tension of thin liquid films: New insight from capillary wave fluctuations

In this paper we review simulation and experimental studies of thermal capillary wave fluctuations as an ideal means for probing the underlying disjoining pressure and surface tensions, and more generally, fine details of the Interfacial Hamiltonian Model. We discuss recent simulation results that reveal a film-height-dependent surface tension not accounted for in the classical Interfacial Hamiltonian Model. We show how this observation may be explained bottom-up from sound principles of statistical thermodynamics and discuss some of its implications.     

On Electrostatics,Covalency, and Chemical Dashes: Physical Interactions versus Chemical Bonds

The increasing availability of real-space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms [see, for instance, Chem. Eur. J. 2018 , 24, 9101] provides evidence for differences between the physicist's concept of interaction and the chemist's concept of a bond. Herein, it is argued that, for the former, all types of interactions are treated equally, whereas, for the latter, only the covalent short-range interactions have actually been used to build intuition about chemical graphs and chemical bonds. This has led to the bonding role of long-range Coulombic terms in molecular chemistry being overlooked. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relationship between these concepts is examined herein, and some notes of caution on how to merge them are proposed.     

Shedding light on the mitochondrial matrix through a functional membrane transporter

The first fluorescent probes that are actively channeled into the mitochondrial matrix by a specific mitochondrial membrane transporter in living cells have been developed. The new functional probes (BCT) have a minimalist structural design based on the highly efficient and photostable BODIPY chromophore and carnitine as a biotargeting element. Both units are orthogonally bonded through the common boron atom, thus avoiding the use of complex polyatomic connectors. In contrast to known mitochondria-specific dyes, BCTs selectively label these organelles regardless of their transmembrane potential and in an enantioselective way. The obtained experimental evidence supports carnitine–acylcarnitine translocase (CACT) as the key transporter protein for BCTs, which behave therefore as acylcarnitine biomimetics. This simple structural design can be readily extended to other structurally diverse starting F-BODIPYs to obtain BCTs with varied emission wavelengths along the visible and NIR spectral regions and with multifunctional capabilities. BCTs are the first fluorescent derivatives of carnitine to be used in cell microscopy and stand as promising research tools to explore the role of the carnitine shuttle system in cancer and metabolic diseases. Extension of this approach to other small-molecule mitochondrial transporters is envisaged.

A BODIPY derivative of carnitine enters mitochondria regardless of their membrane potential and in an enantioselective way through a specific mitochondrial membrane transporter in living cells.