Nucleophilic Reactivity of a Copper(II)–Superoxide Complex

Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, Fe^III–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu^II–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes.     

Copper‐Catalyzed Electrophilic Amination of Heteroarenes and Arenes by CH Zincation

Direct amination of heteroarenes and arenes has been achieved in a one‐pot C? H zincation/copper‐catalyzed electrophilic amination procedure. This amination method provides an efficient and rapid approach to access a diverse range of heteroaromatic and aromatic amines including those previously inaccessible using C? H amination methods. The mild reaction conditions and good functional‐group compatibility demonstrate its great potential for the synthesis of important and complex amines.     

Correlation of the loss in photovoltaic module performance with the ageing behaviour of the backsheets used

The influence of the type of backsheet on the electrical performance of test modules was evaluated before and after increasing time of accelerated ageing (damp heat [DH] exposure). Besides the measurement of the electrical power of the modules and the performance of the cells by electroluminescence, the ageing‐induced changes within the polymeric encapsulate and backsheets were investigated by means of vibrational spectroscopy and by thermo analytical methods. In addition, the permeability of the backsheets in the original and aged state was determined. This wide set of test parameters and methods allowed for the detection of correlations between (i) physical and chemical properties as well as their ageing‐induced changes of the materials and (ii) the module performance. A clear dependence of the relative loss in power output upon exposure under DH conditions for 2000 h could be observed for a set of identical test modules varied in composition only in the type of back cover used. While the modules containing gas‐tight backsheets and glass experienced only little loss in the relative power output, some modules with permeable backsheets showed a significant relative decrease in the power output and fill factor in dependence of the backsheet type used. Cell degradation could be visualised by recording electroluminescence images before and after the accelerated ageing test. The permeation properties of the backsheet used and their ageing‐induced changes seem to have an influence on the module performance. However, the absolute values neither of the water vapour transmission rate (WVTR) nor of the oxygen transmission rate (OTR) are directly linked to the loss in power output upon accelerated ageing under DH conditions. It could be shown that the ageing‐induced changes (relative transmission rates) between WVTR and OTR can be correlated with the module performance. These ageing‐induced changes in the permeation behaviour of the backsheets can be explained by (i) physical changes (e.g. post‐crystallisation, changes in the crystal structure or the crystalline microstructure) and (ii) chemical ageing effects such as a decrease in the molecular mass of the polyester (PET) polymer chains because of hydrolytic polymer degradation leading to a change in the crystallisation behaviour of PET. Hydrolytic degradation (= chemical ageing) of the PET core layer was observed (with varying extent) for all PET‐based backsheets and can, thus, not be directly correlated with the loss in performance of the corresponding test modules. The physical ageing effects, however, were detected only for those backsheets showing (i) strong deviating changes in the relative permeation rates for oxygen and water vapour upon accelerated ageing and (ii) a clear loss in electrical performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Second Comes First: Switching Elementary Steps in Palladium-Catalyzed Cross-Coupling Reactions

The electron-poor palladium(0) complex L₃Pd (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) reacts with Grignard reagents RMgX and organolithium compounds RLi via transmetalation to furnish the anionic organopalladates [L₂PdR]⁻, as shown by negative-ion mode electrospray-ionization mass spectrometry. These palladates undergo oxidative additions of organyl halides R′X (or related S_N2-type reactions) followed by further transmetalation. Gas-phase fragmentation of the resulting heteroleptic palladate(II) complexes results in the reductive elimination of the cross-coupling products RR′. This reaction sequence corresponds to a catalytic cycle, in which the order of the elementary steps of transmetalation and oxidative addition is switched relative to that of palladium-catalyzed cross-coupling reactions proceeding via neutral intermediates. An attractive feature of the palladate-based catalytic system is its ability to mediate challenging alkyl–alkyl coupling reactions. However, the poor stability of the phosphine ligand L against decomposition reactions has so far prevented its successful use in practical applications.     

Effects of diclofenac on EPC liposome membrane properties

In this work the interaction of a non-steroidal anti-inflammatory drug (NSAID), diclofenac, with egg yolk phosphatidylcoline (EPC) liposomes, used as cell-membrane models, was quantified by determination of the partition coefficient. The liposome/aqueous phase partition coefficient was determined by derivative spectrophotometry, fluorescence quenching, and measurement of zeta-potential. Theoretical models based on simple partition of the diclofenac between two different media, were used to fit the experimental data, enabling the determination of K_p. The three techniques used yielded similar results. The effects of the interaction on the membranes characteristics were further evaluated, either by studying membrane potential changes or by effects on membrane fluidity. The liposome membrane potential and the size and size-homogeneity of liposomes were measured by light scattering. The effects of diclofenac on the internal viscosity or fluidity of the membrane were determined by use of spectroscopic probes—a series of n-(9-anthroyloxy) fatty acids in which the carboxyl terminal group is located at the interfacial region of the membrane and the fluorescent anthracene group is attached at different positions along the fatty acid chain. The location of the diclofenac on the membrane was also evaluated, by fluorescence quenching using the same series of fluorescent probes. Because the fluorescent anthracene group is attached at different positions along the fatty acid chain, it is possible to label at a graded series of depths in the bilayer. The interactions between the drug and the probe are a means of predicting the location of the drug on the membrane.     

Investigation of N‐Heterocyclic Carbene‐Supported Group 12 Triflates as Pre‐catalysts for Hydrosilylation/Borylation

N‐Heterocyclic carbene (NHC) complexes of Cd and Hg triflates (OTf) were prepared and their attempted conversion into rare cadmium and mercury hydrides was explored. In contrast to zinc, which forms stable [ZnH]⁺ complexes with NHCs, the heavier Cd and Hg congeners could not be formed; the increased instability of Cd‐H and Hg‐H units was rationalized with the aid of computations. It was also discovered that the dimeric adduct [IPr?Cd(μ‐OTf)₂]₂ (IPr=[(HCNDipp)₂C:]; Dipp=2,6‐iPr₂C₆H₃) is an active precatalyst for the hydrosilylation and hydroborylation of hindered aldehydes and ketones. The related zinc congener was inactive as a catalyst highlighting a distinct advantage of using heavy Group 12 metals to promote catalytic hydrosilylation/borylation.     

Method for three-dimensional data registration from disparate imaging modalities in the NOGA Myocardial Viability Trial

Region-by-region comparison of data concerning left ventricular (LV) status is difficult to perform quantitatively if the data was acquired from disparate imaging modalities. We validated a method for comparing measurements obtained by electromechanical mapping (EMM) catheter with dobutamine stress echocardiography (DSE) via biplane contrast ventriculography, with the assistance of three-dimensional (3-D) echocardiographic data. The ventriculograms were traced and the borders were used to reconstruct the LV in 3-D with the aid of a database of 3-D echocardiographic studies. The 3-D LV was oriented to the EMM data based on the body coordinates and then manually scaled and translated to fit. The EMM data were mapped to the 3-D surface. The 3-D surface was divided into the 16 regions defined for echocardiographic assessment. The mean EMM value for local linear shortening, a parameter of function, was computed in each segment. The EMM and semiquantitative echocardiographic assessments of regional myocardial function were compared by segment, and the volume of the 3-D LV was compared with the volume computed from the ventriculogram. The volume of the 3-D surface correlated closely with that of the ventriculogram (r = 0.97, SEE = 27.4 ml) but with a significant overestimation of 63 +/- 35 ml. There was a highly significant (p < 0.0001) agreement in regional function between EMM and echo. Local linear shortening correlated significantly (p < 0.0001) with echocardiographic severity of wall motion, averaging 9.5 +/- 6.5, 8.1 +/- 5.4, 5.9 +/- 4.8, and 6.2 +/- 3.3 in segments read as normal, hypokinetic, akinetic, and dyskinetic, respectively. The method presented is valid for comparing cardiac parameters derived from disparate image data on a region-by-region basis by employing anatomic landmarks on 3-D reconstructions of the LV endocardial surface.     

Neural activity associated with distinguishing concurrent auditory objects

The neural processes underlying concurrent sound segregation were examined by using event-related brain potentials. Participants were presented with complex sounds comprised of multiple harmonics, one of which could be mistuned so that it was no longer an integer multiple of the fundamental. In separate blocks of trials, short-, middle-, and long-duration sounds were presented and participants indicated whether they heard one sound (i.e., buzz) or two sounds (i.e., buzz plus another sound with a pure-tone quality). The auditory stimuli were also presented while participants watched a silent movie in order to evaluate the extent to which the mistuned harmonic could be automatically detected. The perception of the mistuned harmonic as a separate sound was associated with a biphasic negative-positive potential that peaked at about 150 and 350 ms after sound onset, respectively. Long duration sounds also elicited a sustained potential that was greater in amplitude when the mistuned harmonic was perceptually segregated from the complex sound. The early negative wave, referred to as the object-related negativity (ORN), was present during both active and passive listening, whereas the positive wave and the mistuning-related changes in sustained potentials were present only when participants attended to the stimuli. These results are consistent with a two-stage model of auditory scene analysis in which the acoustic wave is automatically decomposed into perceptual groups that can be identified by higher executive functions. The ORN and the positive waves were little affected by sound duration, indicating that concurrent sound segregation depends on transient neural responses elicited by the discrepancy between the mistuned harmonic and the harmonic frequency expected based on the fundamental frequency of the incoming stimulus.