Inorganic enzyme? Ceria nanoparticles exhibit unique oxidase‐like activity at acidic pH values. These redox catalysts can be used in immunoassays (ELISA) when modified with targeting ligands (see picture; light blue and yellow structures are nanoparticles with attached ligands). This modification allows both for binding and for detection by the catalytic oxidation of sensitive colorimetric dyes (e.g. TMB).
“My favorite subject at school was tennis. When I was eighteen I wanted to be a chemist…?.!” This and more about Manfred T. Reetz can be found on page 3731.
Macrolide magic : An enyne cross‐metathesis reaction of an alkynyl boronate with an alkene derivative as well as a radical cyclization reaction of a homopropargylic β‐alkoxyacrylate are the key transformations in the total synthesis of the cytotoxic macrolide (?)‐amphidinolide K.
Excellent couplings : Recent developments in the metal‐catalyzed C? H activation of sp3 centers in an α position relative to an amine nitrogen atom are presented. Their reaction with alkenes to give alkylamines (hydroaminoalkylation) is also summarized (see general scheme).
Forces to reckon with : Supramolecular complexes, such as the one shown, are normally based on a combination of different interactions such as ion pairing, hydrogen bonds, and stacking interactions. The not always simple characterization of the nature and strength of intermolecular forces provides assistance to the understanding of biomimetic systems, as well as for the design of synthetic receptors, drugs, and intelligent materials.
Last but not least : A simple molecular redox system is used to split water into hydrogen and oxygen photochemically. Two separate photolyses are combined to a cyclic process (see scheme). Osmocene ([Cp2OsII] with Cp?=C5H5?) serves as photocatalyst.
Hooking up : FeCl2 catalyzes the efficient cross dehydrogenative arylation of substrates having benzylic C? H bonds (see scheme). High regioselectivity was observed during the cross‐coupling between compounds containing aromatic C(sp2)? H bonds and benzylic C(sp3)? H bonds. This process is proposed to proceed by single‐electron‐transfer oxidation and Friedel–Crafts alkylation.
Indoles are not indolent : Various indoles react with arylboronic acids chemodivergently. C? H arylation of free indole and N‐methylindole gives the corresponding C(2)‐arylated indoles A whereas N‐acylated, N‐benzoylated, and N‐Boc‐protected indoles provide the corresponding arylcarboaminoxylated products B with excellent diastereoselectivity in good to excellent yields.
Slightly attractive : The attractive and anisotropic nature of the Cl???Cl interaction in C6Cl6 is experimentally demonstrated from an expansion of the electron density ρ( r ) around the chlorine nuclei. The interaction is explained in a model in which there is a bonding attraction involving electron‐deficient (see picture, blue) and electron‐rich (red) regions of adjacent Cl atoms.
All done! A full account of the total synthesis of ouabagenin and ouabain has been described. The synthesis was achieved through a polyanionic cyclization strategy. Degradation studies provide an ultimate proof for a key intermediate observed in the synthesis.
Drei von einer Sorte : Vicinale Tricarbonyl‐Verbindungen gehen Eisen(III)‐vermittelte C‐C‐Spaltungen ein (siehe Schema). Die Ergebnisse sind relevant für den Aminosäurenachweis durch Ninhydrin und für den Vitamin‐C‐Stoffwechsel.
Pass the salt, please! State‐of‐the‐art computations indicate that the stacking complex of a guanine quartet and an adenine quartet (G4A4) can function as a potent ditopic receptor for NaCl in aqueous solution (see picture; Na+, Cl? yellow, O red, N blue, C black, H white).
To study molecular decomposition pathways it is necessary to use ab initio multireference determinant–configuration interaction or MCSCF (multiconfiguration SCF ) calculations. The MRD –CI (multireference double excitation–configuration interaction technique of Buenker and Peyerimhoff) calculations on the decomposition pathway of nitrobenzene were carried out using all of the occupied molecular orbitals in the region of the bond being dissociated, plus all of the virtual orbitals. An effective CI Hamiltonian was used into which were folded the effects of all of the occupied molecular orbitals from which excitations were not allowed. So far we have investigated the lowest 1A1, 3A1, 1A2, 3A2, 1B1, 3B1, 1B2, 3B2 states and are investigating the higher states. Our results show a wealth of structure in the potential energy surfaces for the various electronic states of nitrobenzene as a function of distance. A number of the states are predissociative and change dominant configuration one or more times along these potential energy surfaces. 相似文献
Long‐distance service : Finding a selective small‐molecule modulator for every domain of every human protein is a Herculean task. Wouldn't it be much easier to control the activity of any protein of choice by simply fusing it with a generally adaptable switch protein and controlling protein activity indirectly?
Bright funnels : A series of dendritic systems, which are capable of funneling energy from the periphery to the core, have been synthesized. The photophysical properties of dendrimers have been determined. Selective excitation of the donor leads to an efficient energy transfer (>90 %) to the acceptor. The approach provides a facile synthesis for the modification of near‐infrared BF2‐Azadipyrromethenes.
