Cooperative Lewis Pairs Based on Late Transition Metals: Activation of Small Molecules by Platinum(0) and B(C6F5)3

A Lewis basic platinum(0)–CO complex supported by a diphosphine ligand and B(C₆F₅)₃ act cooperatively, in a manner reminiscent of a frustrated Lewis pair, to activate small molecules such as hydrogen, CO₂, and ethene. This cooperative Lewis pair facilitates the coupling of CO and ethene in a new way.     

Direct Imaging of Octahedral Distortion in a Complex Molybdenum Vanadium Mixed Oxide

Complex Mo,V‐based mixed oxides that crystallize in the orthorhombic M1‐type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X‐ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively.     

Whole‐Genome Sequencing of a Single Viral Species from a Highly Heterogeneous Sample

Metagenomic studies suggest that only a small fraction of the viruses that exist in nature have been identified and studied. Characterization of unknown viral genomes is hindered by the many genomes populating any virus sample. A new method is reported that integrates drop‐based microfluidics and computational analysis to enable the purification of any single viral species from a complex mixed virus sample and the retrieval of complete genome sequences. By using this platform, the genome sequence of a 5243 bp dsDNA virus that was spiked into wastewater was retrieved with greater than 96 % sequence coverage and more than 99.8 % sequence identity. This method holds great potential for virus discovery since it allows enrichment and sequencing of previously undescribed viruses as well as known viruses.     

The Unexpected Influence of Precursor Conversion Rate in the Synthesis of III–V Quantum Dots

Control of quantum dot (QD) precursor chemistry has been expected to help improve the size control and uniformity of III–V QDs such as indium phosphide and indium arsenide. Indeed, experimental results for other QD systems are consistent with the theoretical prediction that the rate of precursor conversion is an important factor controlling QD size and size distribution. We synthesized and characterized the reactivity of a variety of group‐V precursors in order to determine if precursor chemistry could be used to improve the quality of III–V QDs. Despite slowing down precursor conversion rate by multiple orders of magnitude, the less reactive precursors do not yield the expected increase in size and improvement in size distribution. This result disproves the widely accepted explanation for the shortcoming of current III–V QD syntheses and points to the need for a new generalizable theoretical picture for the mechanism of QD formation and growth.     

A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling

Metal ion signaling in biology has been studied extensively with ortho‐nitrobenzyl photocages; however, the low quantum yields and other optical properties are not ideal for these applications. We describe the synthesis and characterization of NTAdeCage, the first member in a new class of Zn²⁺ photocages that utilizes a light‐driven decarboxylation reaction in the metal ion release mechanism. NTAdeCage binds Zn²⁺ with sub‐pM affinity using a modified nitrilotriacetate chelator and exhibits an almost 6 order of magnitude decrease in metal binding affinity upon uncaging. In contrast to other metal ion photocages, NTAdeCage and the corresponding Zn²⁺ complex undergo efficient photolysis with quantum yields approaching 30 %. The ability of NTAdeCage to mediate the uptake of ⁶⁵Zn²⁺ by Xenopus laevis oocytes expressing hZIP4 demonstrates the viability of this photocaging strategy to execute biological assays.     

Perovskites with the Framework‐Forming Xenon

The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO₆) (M=Ca, Sr, Ba) containing framework‐forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner‐sharing (XeO₆) and (NaO₆) octahedra arranged in a three‐dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated Xe^VIII and Si^IV exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that Xe^VIII can be incorporated into hyperbaric frameworks such as MgSiO₃ perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas.     

New approach for natural products screening by real-time monitoring of hemoglobin hydrolysis using quartz crystal microbalance

The hemoglobin (Hb) released from erythrocytes is a primary nutritive component for many blood-feeding parasites. The aspartic protease cathepsin D is a hemoglobinase that is involved in the Hb degradation process and is considered an interesting target for chemotherapy intervention. However, traditional enzymatic assays for studying Hb degradation utilize spectrophotometric techniques, which do not allow real-time monitoring and can present serious interference problems. Herein, we describe a biosensor using simple approach for the real-time monitoring of Hb hydrolysis as well as an efficient screening method for natural products as enzymatic inhibitors using a quartz crystal microbalance (QCM) technique. Hemoglobin was anchored on the quartz crystal surface using mixed self-assembled monolayers. The addition of the enzyme caused a mass change (frequency shift) due to Hb hydrolysis, which was monitored in real time. From the frequency change patterns of the Hb-functionalized QCM, we evaluated the enzymatic reaction by determining the kinetic parameters of product formation (k_cat). The QCM enzymatic assay using immobilized human Hb was shown to be an excellent approach for screening possible inhibitors in complex mixtures, opening up a new avenue for the discovery of novel inhibitors.