Innenrücktitelbild: Manganese‐Catalyzed Direct Nucleophilic C(sp2)?H Addition to Aldehydes and Nitriles (Angew. Chem. 46/2015)

Herein, a manganese‐catalyzed nucleophilic addition of inert C(sp²) H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy. The reactions feature mild reaction conditions, excellent regio‐ and stereoselectivity, and a wide substrate scope, which includes both aromatic and olefinic C H bonds, as well as a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.     

Nanobody-based electrochemical immunoassay for Bacillus thuringiensis Cry1Ab toxin by detecting the enzymatic formation of polyaniline

We describe an electrochemical immunoassay for the Cry1Ab toxin that is produced by Bacillus thuringiensis. It is making use of a nanobody (a heavy-chain only antibody) that was selected from an immune phage displayed library. A biotinylated primary nanobody and a HRP-conjugated secondary nanobody were applied in a sandwich immunoassay where horseradish peroxidase (HRP) is used to produce polyaniline (PANI) from aniline. PANI can be easily detected by differential pulse voltammetry at a working voltage as low as 40 mV (vs. Ag/AgCl) which makes the assay fairly selective. This immunoassay for Cry1Ab has an analytical range from 0.1 to 1000 ng∙mL^-1 and a 0.07 ng∙mL^-1 lower limit of detection. The average recoveries of the toxin from spiked samples are in the range from 102 to 114 %, with a relative standard deviation of <7.5 %. The results demonstrated that the assay represented an attractive alternative to existing immunoassays in enabling affordable, sensitive, robust and specific determination of this toxin.

Nanobodies specific to Cry1Ab toxin were isolated from an immunized camel. A biotinylated primary nanobody and a HRP-conjugated secondary nanobody were applied in a sandwich immunoassay with horseradish peroxidase being used to produce polyaniline, which can be easily detected by differential pulse voltammetry.

     

Two new chalcones from Shuteria sinensis

Two new chalcones, 2′,3,4,4′-tetrahydroxy-2-prenylchalcone (1) and 3-methoxy-2′,4,4′-trihydroxy-2-prenylchalcone (2), together with two known compounds, munsericin (3) and 3,4-dihydroxylonchocarpin (4), were isolated from the ethanol extract of the whole plant of Shuteria sinensis. Their structures were identified by spectroscopic analysis methods, such as 1D and 2D NMR, along with HR-MS data. Glucose metabolism activity of four compounds was tested, compounds 3 and 4 showed effect on the glucose consumption of insulin-resistant HepG2 cells.     

Iron(III)‐Selective Chelation‐Enhanced Fluorescence Sensing for In Vivo Imaging Applications

A “turn‐on” pattern Fe³⁺‐selective fluorescent sensor was synthesized and characterized that showed high fluorescence discrimination of Fe³⁺ over Fe²⁺ and other tested ions. With a 62‐fold fluorescence enhancement towards Fe³⁺, the probe was employed to detect Fe³⁺ in vivo in HeLa cells and Caenorhabditis elegans, and it was also successfully used to elucidate Fe³⁺ enrichment and exchange infected by innexin3 (Inx3) in hemichannel‐closed Sf9 cells.     

Altering the Position of Phenyl Substitution to Adjust Film Morphology and Memory Device Performance

In this study, two structural isomers α‐PBT and β‐PBT, which only differ in the phenyl substituent position on the quinoline chromophore, have been designed and successfully synthesized. The influences of substituent position on the film morphology and the storage performance of the devices were investigated. Both molecules employed in the memory devices exhibited same nonvolatile binary (write‐once‐read‐many‐times; WORM) characteristics, but the switch threshold voltage (Vth) of the β‐PBT‐based device was clearly lower than that of the α‐PBT‐based device. Simulation results demonstrate that the variation of the phenyl substituent position led to different intermolecular stacking styles and thus to varied grain sizes for each film morphology. This work illustrates that altering the phenyl substituent position on the molecular backbone could improve the quality of the film morphology and reduce power consumption, which is good for the rational design of future advanced organic memory devices (OMDs).     

Selective adsorption of metronidazole on conjugated microporous polymers

Conjugated microporous polymers (CMPs) have recently received extensive attention in oil/organic solvent-water separation field as a kind of ideal porous absorbents with tunable porosity, large surface areas, and super-hydrophobicity. However, reports on the application of CMPs in adsorption of hydrophilic contaminants from water are very few. In this work, we studied the adsorption of metronidazole (MNZ), a polar antibiotic, by two kinds of CMPs. The adsorption characteristics of MNZ by the CMPs, including adsorption kinetics, mechanism, and isotherm parameters were calculated. The adsorption kinetics of MNZ was well expressed by the pseudo-second-order model, and the adsorption process was found to be mainly controlled by film diffusion. The adsorption isotherm data agreed well with the Langmuir isotherm model, and the values of free energy E indicated that the adsorption nature of MNZ on the CMPs was physisorption. Increasing dispersion degree of the CMPs in MNZ solution resulted in greater adsorption. This work may provide fundamental guidance for the removal of antibiotics by CMPs.     

High-internal-phase-emulsion polymeric monolith coupled with liquid chromatography–electrospray tandem mass spectrometry for enrichment and sensitive detection of trace cytokinins in plant samples

High-internal-phase-emulsion polymers (polyHIPEs) show great promise as solid-phase-extraction (SPE) materials because of the tremendous porosity and highly interconnected framework afforded by the high-internal-phase-emulsion (HIPE) technique. In this work, polyHIPE monolithic columns as novel SPE materials were prepared and applied to trace enrichment of cytokinins (CKs) from complex plant samples. The polyHIPE monoliths were synthesized via the in-situ polymerization of the continuous phase of a HIPE containing styrene (STY) and divinylbenzene (DVB) in a stainless column, and revealed highly efficient and selective enrichment ability for aromatic compounds. Under the optimized experimental conditions, a method using a monolithic polyHIPE column combined with liquid chromatography–electrospray tandem mass spectrometry (LC–MS–MS) was developed for the simultaneous extraction and sensitive determination of trans-zeatin (tZ), meta-topolin (mT), kinetin (K), and kinetin riboside (KR). The proposed method had good linearity, with correlation coefficients (R ²) from 0.9957 to 0.9984, and low detection limits (LODs, S/N?=?3) in the range 2.4–47 pg mL^?1 for the four CKs. The method was successfully applied to the determination of CKs in real plant samples, and obtained good recoveries ranging from 68.8 % to 103.0 % and relative standard deviations (RSDs) lower than 16 %.     

The X<Superscript>−</Superscript>···benzohydrazide complexes: the interplay between anion-π and H-bond interactions

The compounds containing the benzohydrazide (BH) nucleus have a variety of biological activities because of various noncovalent intermolecular interactions. The interplay between anion-π and H-bond interactions, which can affect the activity of compounds, has been investigated in ten substituted BH exposed to the chloride ion using the quantum mechanical calculations. The total interaction energy is separated into the anion-π (ΔE _Aπ) and H-bond (ΔE _HB) contributions where both interactions are presented in the complexes. The electron-withdrawing substituents (EWSs) increase |ΔE _Aπ| and decrease |ΔE _HB|, while reversed changes are observed with the electron-donating substituents (EDSs). In addition, the total binding energy (ΔE) becomes more/less negative in the presence of EWSs/EDSs. The synergetic effects of mentioned interactions and substituent effects have also been investigated using the atoms in molecules (AIM), natural bond orbital (NBO) and molecular electrostatic potential (MEP) analyses. A good correlation is found between the energy data and the Hammett constants, the minimum of electrostatic potential (V _min) and the results of population analyses.     

DFT studies on the acid-catalyzed Curtius reaction: the Schmidt reaction

The Schmidt reaction is the acid-catalyzed analogue of the Curtius reaction and is extensively used in organic synthesis. In this work, the mechanism of this reaction has been explored using DFT calculations at the B3LYP/6-311+G(d,p) level. Protonated formyl azide may undergo rearrangement to the product, protonated isocyanic acid, with simultaneous extrusion of molecular nitrogen (concerted mechanism), or undergo rearrangement to the anti conformer, followed by removal of nitrogen to form the nitrenium ion, which then rearranges to the final product, protonated isocyanic acid (step-wise mechanism). Like the Curtius reaction, it is found that the concerted pathway is definitely preferred. The key role of acidification in decreasing the overall energy barrier is more highlighted in case of phenyl substitution, with negligible effect on the lower homologues. For methoxy and amine substituents, there is very little difference in the activation energies of the concerted and step-wise reactions, with the former being still slightly preferred. Unlike the parent compound, the rearrangement of substituted nitrenium ion in some cases involves side reactions like C-H insertion and cyclization.     

Are metals made from molecules?

In the traditional view, covalently bound materials differ in a fundamental way from metallic substances. Though both are built from more basic units that are, in turn, constructed from a small number of atoms, for these two materials classes the nature of these units is thought to be quite different. For covalent solids and liquids, these units are considered to be molecular, meaning that they possess properties and bonding that are retained in the condensed phase and thus they continue to be identifiable within the larger system. For metallic materials, these basic units are considered to be mere constructs that are not observable against the delocalized bonding of metals or alloys. The perceived dissimilarity of metallic and covalently bound materials has fostered distinctly different approaches to their design and improvement. Here, the delocalized view of metallic bonding is examined. This examination suggests that much of the rationale used in the design of molecular materials my be applied to metals and alloys as well.