Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom

The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [Co^IIIW₁₂O₄₀]^5? as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H₂O→ArOH+H₂. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO₂ and H₂ is a side‐reaction.     

Site-specific conjugation of ScFvs antibodies to nanoparticles by bioorthogonal strain-promoted alkyne-nitrone cycloaddition

Particularly suitable: An N-terminal serine mutant of anti-HER2 scFv antibody was conjugated to polymer-coated magnetofluorescent nanoparticles by strain-promoted alkyne-nitrone cycloaddition. The resulting nanoparticles (see scheme) proved effective in targeting and labeling HER2-positive breast cancer cells.     

Factors controlling the drop evaporation constant

In this paper, we discuss the factors affecting drop evaporation. We found that the droplet morphology at a specific temperature was controlled by the physical properties of the liquid itself, such as the molecular weight, density, diffusion coefficient in air, and heat of vaporization. Two processes are included in drop evaporation: diffusion of liquid molecules into the air (diffusion part) and flow of the liquid molecules from inside the drop to the free outer shell liquid layer within the liquid-vapor interface (evaporation part). The diffusion part remained steady during drying and was not sensitive to the variation of temperature. The evaporation part, however, was an active factor and determined the differences in drop evaporation behaviors.     

A stereoselective and atom-efficient approach to multifunctionalized five- and six-membered rings via a novel michael-initiated intramolecular Diels-Alder furan reaction

[reaction: see text] A variety of key precursors to the intramolecular Diels-Alder reaction of furan diene (IMDAF) have been prepared via a very facile 1,4-addition of O-, S-, N-, and C-centered nucleophiles possessing unsaturated tether to beta-furyl nitroethylene. Subsequent IMDAF reaction of the 1,4-adducts, carried out under thermal conditions, provided five- and six-membered carbocycles and heterocycles fused to an easily cleavable oxabicycloheptene moiety. The structure and stereochemistry of the cycloadducts were determined by 2D-NMR experiments and further confirmed by X-ray crystallography. The salient features of the strategy include high degree of stereoselectivity (>80:20) in the cycloaddition, atom and step economy, and generation of multiple chiral centers and functionalities. The feasibility of the cleavage of the oxa bridge in the cycloadducts to afford novel multifunctional molecules has also been demonstrated.     

NMR-assisted computational studies of peptidomimetic inhibitors bound in the hydrophobic pocket of HIV-1 glycoprotein 41

Due to the inherently flexible nature of a protein–protein interaction surface, it is difficult both to inhibit the association with a small molecule, and to predict how it might bind to the surface. In this study, we have examined small molecules that mediate the interaction between a WWI motif on the C-helix of HIV-1 glycoprotein-41 (gp41) and a deep hydrophobic pocket contained in the interior N-helical trimer. Association between these two components of gp41 leads to virus–cell and cell–cell fusion, which could be abrogated in the presence of an inhibitor that binds tightly in the pocket. We have studied a comprehensive combinatorial library of α-helical peptidomimetics, and found that compounds with strongly hydrophobic side chains had the highest affinity. Computational docking studies produced multiple possible binding modes due to the flexibility of both the binding site and the peptidomimetic compounds. We applied a transferred paramagnetic relaxation enhancement experiment to two selected members of the library, and showed that addition of a few experimental constraints enabled definitive identification of unique binding poses. Computational docking results were extremely sensitive to side chain conformations, and slight variations could preclude observation of the experimentally validated poses. Different receptor structures were required for docking simulations to sample the correct pose for the two compounds. The study demonstrated the sensitivity of predicted poses to receptor structure and indicated the importance of experimental verification when docking to a malleable protein–protein interaction surface.     

Mycotoxin profile of Fusarium langsethiae isolated from wheat in Italy: production of type‐A trichothecenes and relevant glucosyl derivatives

Fusarium langsethiae, formally described as a new species over a decade ago, has been identified as the main producer of HT‐2 (HT2) and T‐2 (T2) toxins in Europe in small cereal grains. Mycotoxin contamination caused by this Fusarium species can represent a food safety hazard that deserves further attention. In the present work, the mycotoxin profile in wheat cultures of F. langsethiae is presented with particular reference to the production of major type‐A trichothecenes and their glucosyl derivatives. F. langsethiae isolates, representative of the major Italian wheat cultivation areas, were tested for the production of T2, HT2, diacetoxyscirpenol (DAS) and neosolaniol (NEO), and relevant glucosyl derivatives. Liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) was used for the identification and chemical characterization of these metabolites. F. langsethiae isolates under investigation resulted to be potent producers of T2, HT2 and NEO. Furthermore, a well‐defined set of isolates, all originating from Central Italy, produced also DAS. All isolates were found to be able to produce HT2 glucosyl derivatives, whereas only traces of T2 glucoside were detected in one sample. Furthermore, two mono‐glucosyl derivatives of NEO and one mono‐glucoside derivative of DAS were identified and characterized. The screening for the presence/absence of glucosylated trichothecenes in analyzed fungal extracts revealed a general co‐occurrence of these derivatives with the parent toxin at levels that could be roughly estimated to account up to 37% of the relevant unconjugated toxin. This is the first report of the production of glucosylated trichothecenes by F. langsethiae cultured on small grains. Copyright © 2013 John Wiley & Sons, Ltd.     

Tentoxin as a scaffold for drug discovery. Total solid-phase synthesis of tentoxin and a library of analogues

[reaction: see text] A solid-phase method for the synthesis of tentoxin has been developed. Two key steps-dehydration and N-alkylation-are carried out while the peptide is anchored to the resin. The method, which has been validated by the preparation of a library of tentoxin analogues, should be applicable to the generation of further libraries that have the tentoxin scaffold structure, as well as other structures containing N-alkylated didehydroamino acids.     

Bioinspired synthesis of new silica structures

Silicon and oxygen are the two most abundant elements in the Earth's crust but despite the vast scientific literature on crystalline and amorphous silica, new chemistries, structures and applications continue to be discovered for compounds formed from these elements--thus we present here for the first time the formation of new amorphous silica structures that were uniquely synthesized by a bioinspired synthetic system.     

Halogen Bonding Assembles Anion⋅⋅⋅Anion Architectures in Non-centrosymmetric Iodate and Bromate Crystals

Single crystal X-ray diffraction of iodate and bromate salts shows that the I and Br atoms in IO₃⁻ and BrO₃⁻ anions form short and linear O−I/Br ⋅⋅⋅ O contacts with the O atoms of nearby anions. Non-centrosymmetric systems are formed wherein anions are orderly aligned into supramolecular 1D and 2D networks. Theoretical evidences, namely the outcome of QTAIM and NCIplot studies, prove the attractive nature of these contacts and the ability of iodate and bromate anions to act as robust halogen bond (HaB) donors. The HaB is proposed as a general and effective assisting tool to control the architecture of acentric iodate salts.