Nickel‐Catalyzed Cross‐Coupling of Redox‐Active Esters with Boronic Acids

A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross‐coupling between alkyl‐carboxylic acids and boronic acids is described. This Ni‐catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox‐active ester derivatives, specifically N‐hydroxy‐tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl₂?6 H₂O—$9.5 mol^?1, Et₃N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption.     

Protein-nanoparticle labelling probed by surface enhanced resonance Raman spectroscopy

A benzotriazole dye has been attached to a heme protein via a Michael addition and the unique potential of surface enhanced resonance Raman scattering (SERRS) to provide informative in situ recognition of more than one label on one protein demonstrated.     

Investigation into the factors affecting accuracy of mass measurements on a time-of-flight mass spectrometer using Design of Experiment

The results of an investigation of the parameters which have the most significant effect on the accuracy of mass measurements on a quadrupole orthogonal acceleration time-of-flight mass spectrometer (q-oaToF) are reported. The influence of eight factors is investigated: ion abundances of reference and analyte compounds, mass difference between analyte and reference compounds, quality of calibration, number of reference acquisitions averaged and TDC (time-to-digital converter) settings (resolution, Np multiplier (number of pushes correction factor), minimum number of points, i.e. minimum acquisition width which defines a peak). To extract the maximum information from as few experiments as possible, a Design of Experiment approach was used. The data will be used as a basis for developing guidance on accurate mass measurement on q-oaToF instruments.     

Time correlations and the second entropy

The authors study the transport of mass and heat in simulations of a Lennard-Jones fluid and demonstrate the calculation of transport coefficients, and of both the first and second entropies. These entropies are calculated from time correlation functions, as are the transport coefficients. They discuss the role of the second entropy in providing a physical explanation for the link between dynamic fluctuations and response. They illustrate the physical significance of the various contributions to the second entropy and how they simplify in the case of relaxation by steady-state flow. Certain approximations proposed for the calculation of the first entropy, common in the literature, are shown to break down under certain circumstances, and they give an improved method of calculation. They pay particular attention to the coupling between variables of opposite time parity in the transport matrix, and show that in general this cannot be neglected.     

In-situ study of the catalytic oxidation of CO on a Pt(1 1 0) surface using ambient pressure X-ray photoelectron spectroscopy

CO and O₂ co-adsorption and the catalytic oxidation of CO on a Pt(1 1 0) surface under various pressures of CO and O₂ (up to 250 mTorr) are studied using ambient pressure X-ray photoelectron spectroscopy (APXPS) and mass spectrometry. There is no surface oxide formation on Pt under our reaction conditions. CO oxidation in this pressure (<500 mTorr), O₂ to CO ratio (<10), and temperature (150 °C) regime is consistent with the Langmuir-Hinshelwood reaction mechanism. Our findings provide in-situ surface chemical composition data of the catalytic oxidation of CO on Pt(1 1 0) at total pressures below 1 Torr.     

In situ growth of polymer electrolytes on lithium ion electrode surfaces

Polyacrylonitrile (PAN) films were grown on glassy carbon, nickel foam and MnO₂ substrates by cathodic electropolymerisation of acrylonitrile in acetonitrile with tetrabutylammonium perchlorate (TBAP) as the supporting electrolyte. The electronic barrier properties of the films were confirmed by impedance spectroscopy of carbon |PAN| Hg cells while the ionic resistance of the films varied from 200 kΩ cm² in the dry state to 1.4 Ω cm² when plasticised with 1 M LiPF₆ in propylene carbonate. A galvanic cell was prepared by successive electrodepositions of MnO₂ and PAN on a carbon substrate, using liquid lithium amalgam as the top contact. The cell showed a stable open circuit potential and behaved normally under the galvanostatic intermittent titration technique (GITT).     

Redox Economy in Organic Synthesis

Stimulus package for organic synthesis : The economy of step and atom usage has been widely reviewed and acknowledged as being useful frameworks to evaluate the efficiency of synthesis. This Review brings to attention another form of economy which should be considered in the planning and evaluation of a multistep synthesis: redox economy. Several guidelines and examples are included to illustrate the logic of this approach and to stimulate the design of syntheses.

     

Stereodivergent Synthesis of 17‐α and 17‐β‐Aryl Steroids: Application and Biological Evaluation of D‐Ring Cortistatin Analogues

One stereocenter makes all the difference : The synthesis and biological evaluation of 17‐epi‐cortistatin A is reported from a common intermediate used to procure natural cortistatin A. The synthesis features a unique stereocontrolled Raney‐Ni reduction process that can be employed to reliably produce both α‐ and β‐configured D‐ring aryl steroids. Biological evaluations of these “cortalogs” are reported for the first time.

     

Sampling systems for isotope-ratio mass spectrometry of atmospheric ammonia

Passive and active ammonia (NH(3)) sampling devices have been tested for their nitrogen (N) capture potential and delta(15)N fractionation effects. Several sampling techniques produced significantly different delta(15)NH(3) signals when sampling the same NH(3) source released from field site fumigation campaigns. Conventional passive NH(3)-monitoring systems have shown to provide insufficient N for isotope-ratio mass spectrometry and various modified devices have been developed, based on existing diffusion tube designs, to overcome this problem. The final sampler design was then tested in a wind tunnel to verify that sampling NH(3) in different environmental conditions did not significantly fractionate the delta(15)N signal.