Galactose Oxidase/Prussian Blue Based Biosensors

This paper describes the development of an amperometric biosensor based on galactose oxidase (GAOx) immobilization within a laponite clay film deposited on Carbon Screen‐Printed Electrodes modified by electrodeposited Prussian Blue and coated with poly‐(O‐phenylenediamine) (PPD/PB/CSPEs). Amperometric performances of GAOx@laponite/PPD/PB/CSPEs bioelectrodes were determined using several GAOx substrates. Using these modified electrodes the reduction of enzymatically generated hydrogen peroxide was performed at ?0.2 V vs. Ag‐AgCl. In an initial attempt, E.Coli transketolase activity on its immobilized form was followed using a bienzymatic GAOx‐TK biosensor.     

Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

Higher homologues of widely reported C₈₆ isoprenoid diglycerol tetraether lipid cores, containing 0–6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography‐tandem mass spectrometry confirms that the additional carbon atoms in the C_87‐88 homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl (‘H‐shaped’) tetraethers containing C_40‐42 or C_81‐82 hydrocarbons, respectively, many representing novel compounds. Gas chromatography‐mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C₄₀ chains are biphytanes and the C₄₁ chains 13‐methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di‐ and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C_87‐89 tetraethers highlight their potential as complementary biomarkers for archaea in natural environments. Copyright © 2015 John Wiley & Sons, Ltd.     

Selective Aptamer‐Based Control of Intraneuronal Signaling

Cellular behavior is orchestrated by the complex interactions of a myriad of intracellular signal transduction pathways. To understand and investigate the role of individual components in such signaling networks, the availability of specific inhibitors is of paramount importance. We report the generation and validation of a novel variant of an RNA aptamer that selectively inhibits the mitogen‐activated kinase pathway in neurons. We demonstrate that the aptamer retains function under intracellular conditions and that application of the aptamer through the patch‐clamp pipette efficiently inhibits mitogen‐activated kinase‐dependent synaptic plasticity. This approach introduces synthetic aptamers as generic tools, readily applicable to inhibit different components of intraneuronal signaling networks with utmost specificity.     

Engineering Rieske Non‐Heme Iron Oxygenases for the Asymmetric Dihydroxylation of Alkenes

The asymmetric dihydroxylation of olefins is of special interest due to the facile transformation of the chiral diol products into valuable derivatives. Rieske non‐heme iron oxygenases (ROs) represent promising biocatalysts for this reaction as they can be engineered to efficiently catalyze the selective mono‐ and dihydroxylation of various olefins. The introduction of a single point mutation improved selectivities (≥95 %) and conversions (>99 %) towards selected alkenes. By modifying the size of one active site amino acid side chain, we were able to modulate the regio‐ and stereoselectivity of these enzymes. For distinct substrates, mutants displayed altered regioselectivities or even favored opposite enantiomers compared to the wild‐type ROs, offering a sustainable approach for the oxyfunctionalization of a wide variety of structurally different olefins.     

Synthesis of 2‐Unsubstituted 1,3‐Selenazoles by Cyclization of Selenoformamide with α‐Bromocarbonyl Compounds

2‐Unsubstituted 1,3‐selenazoles were prepared by cyclization of selenoformamide with α‐bromoacetophenones. Parent 1,3‐selenazole was prepared by cyclization of selenoformamide with α‐bromoacetaldehyde.     

Linked Supramolecular Building Blocks for Enhanced Cluster Formation

Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.     

Facile Interchange of 3d and 4f Ions in Single‐Molecule Magnets: Stepwise Assembly of [Mn4], [Mn3Ln] and [Mn2Ln2] Cages within Calix[4]arene Scaffolds

The central Mn^II ions in a series of calix[4]arene‐stabilised butterflies can be sequentially replaced with Ln^III ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of Mn^II for Gd^III allows for the examination of the transferability of spin‐Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low‐lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single‐ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TM^II/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p‐tBu‐calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different “guests” within structurally robust “hosts”.     

BODIPY: A Highly Versatile Platform for the Design of Bimodal Imaging Probes

In molecular imaging, multimodal imaging agents can provide complementary information, for improving the accuracy of disease diagnosis or enhancing patient management. In particular, optical/nuclear imaging may find important preclinical and clinical applications. To simplify the preparation of dual‐labeled imaging agents, we prepared versatile monomolecular multimodal imaging probe (MOMIP) platforms containing both a fluorescent dye (BODIPY) and a metal chelator (polyazamacrocycle). One of the MOMIP was conjugated to a cyclopeptide (i.e., octreotide) and radiolabeled with ¹¹¹In. In vitro and in vivo studies of the resulting bioconjugate were conducted, highlighting the potential of these BODIPY‐based bimodal probes. This work also confirmed that the biovector and/or the bimodal probes must be chosen carefully, due to the impact of the MOMIP on the overall properties of the resulting imaging agent.