Evidence for Non-Innocence of a β-Diketonate Ligand

β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac⁻) to Cr^II spontaneously affords Cr^III and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry.     

Click Chemistry Mediated Functionalization of Vertical Nanowires for Biological Applications

Semiconductor nanowires (NWs) are gaining significant importance in various biological applications, such as biosensing and drug delivery. Efficient and controlled immobilization of biomolecules on the NW surface is crucial for many of these applications. Here, we present for the first time the use of the Cu^I‐catalyzed alkyne–azide cycloaddition and its strain‐promoted variant for the covalent functionalization of vertical NWs with peptides and proteins. The potential of the approach was demonstrated in two complementary applications of measuring enzyme activity and protein binding, which is of general interest for biological studies. The attachment of a peptide substrate provided NW arrays for the detection of protease activity. In addition, green fluorescent protein was immobilized in a site‐specific manner and recognized by antibody binding to demonstrate the proof‐of‐concept for the use of covalently modified NWs for diagnostic purposes using minute amounts of material.     

Investigating the Disordered and Membrane-Active Peptide A-Cage-C Using Conformational Ensembles

The driving forces and conformational pathways leading to amphitropic protein-membrane binding and in some cases also to protein misfolding and aggregation is the subject of intensive research. In this study, a chimeric polypeptide, A-Cage-C, derived from α-Lactalbumin is investigated with the aim of elucidating conformational changes promoting interaction with bilayers. From previous studies, it is known that A-Cage-C causes membrane leakages associated with the sporadic formation of amorphous aggregates on solid-supported bilayers. Here we express and purify double-labelled A-Cage-C and prepare partially deuterated bicelles as a membrane mimicking system. We investigate A-Cage-C in the presence and absence of these bicelles at non-binding (pH 7.0) and binding (pH 4.5) conditions. Using in silico analyses, NMR, conformational clustering, and Molecular Dynamics, we provide tentative insights into the conformations of bound and unbound A-Cage-C. The conformation of each state is dynamic and samples a large amount of overlapping conformational space. We identify one of the clusters as likely representing the binding conformation and conclude tentatively that the unfolding around the central W23 segment and its reorientation may be necessary for full intercalation at binding conditions (pH 4.5). We also see evidence for an overall elongation of A-Cage-C in the presence of model bilayers.     

An Aldehyde Responsive,Cleavable Linker for Glucose Responsive Insulins

A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals.     

Ortho lithiation-in situ borylation of substituted morpholine benzamides

Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic esters as the major isomer (>90% regioselectivity) in crude isolated yields ranging from 68 to 93%. The synthetic usability of such building blocks was subsequently illustrated via the synthesis of a kinase inhibitor.     

A comparative study of fluorine substituents for enhanced stability of flexible and ITO‐free high‐performance polymer solar cells

Two low‐band gap polymer series based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and dithienylbenzothiadiazole, with different numbers of fluorine substituents on the 2,3,1‐benzothiadiazole unit, have been synthesized and explored in a comparative study of the photochemical stability and operational lifetime in flexible large area roll‐coated bulk heterojunction solar cells. The two polymer series have different side chains on the BDT unit, namely 2‐hexyldecyloxy (BDT_HDO) ( P1–P3 ) or 2‐hexyldecylthiophene (BDT_THD) ( P4–P6 ). The photochemical stability clearly shows that the stability enhances along with the number of fluorine atoms incorporated on the polymer backbone. Fabrication of the polymer solar cells based on the materials was carried out in ambient atmosphere on a roll coating/printing machine employing flexible and indium‐tin‐oxide‐free plastic substrates. Solar cells based on the P4–P6 series showed the best performance, reaching efficiencies up to 3.8% for an active area of 1 cm², due to an enhanced current compared to P1–P3 . Lifetime measurements, carried out according to international summit on OPV stability (ISOS), of encapsulated devices reveals an initial fast decay for P1–P6 in the performance followed by a much slower decay rate, still retaining 40–55% of their initial performance after 250 h of testing under ISOS‐L‐1 conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 893–899