Towards a Zinc‐Catalyzed Asymmetric Hydrogenation/Transfer Hydrogenation of Imines

The first asymmetric hydrogenation/transfer hydrogenation of imines to amines using zinc(II) triflate in combination with chiral ligands is described. The monodentate binaphthophosphepine ligand ( 3g ) provided the highest enantioselectivities. Using different imines, the corresponding amines were obtained in moderate yields and enantioselectivities.     

Adsorption and thermal decomposition of 2-octylthieno[3,4-b]thiophene on Au(111)

The adsorption and thermal stability of 2-octylthieno[3,4-b]thiophene (OTTP) on the Au(111) surfaces have been studied using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). UHV-STM studies revealed that the vapor-deposited OTTP on Au(111) generated disordered adlayers with monolayer thickness even at saturation coverage. XPS and TPD studies indicated that OTTP molecules on Au(111) are stable up to 450K and further heating of the sample resulted in thermal decomposition to produce H(2) and H(2)S via C-S bond scission in the thieno-thiophene rings. Dehydrogenation continues to occur above 600K and the molecules were ultimately transformed to carbon clusters at 900K. Highly resolved air-STM images showed that OTTP adlayers on Au(111) prepared from solution are composed of a well-ordered and low-coverage phase where the molecules lie flat on the surface, which can be assigned as a (9×2√33)R5° structure. Finally, based on analysis of STM, TPD, and XPS results, we propose a thermal decomposition mechanism of OTTP on Au(111) as a function of annealing temperature.     

Structural Aspects of Copper‐Mediated Atom Transfer Radical Polymerization with a Novel Tetradentate Bisguanidine Ligand

This contribution reports the synthesis of the novel tetradentate bisguanidine ligand 2′,2′‐[ethane‐1, 2‐diylbis(methylazanediyl)]bis(ethane‐2, 1‐diyl)bis(1, 1, 3, 3‐tetramethylguanidine) ( L1 , TMG₂dmtrien), which combines two weak amine and two strong guanidine donor functions. Two new copper(II) complexes were isolated and structurally characterized as complexes [Cu(TMG₂dmtrien)][Br]₂ · 3MeCN ( C1 [Br]₂ · 3MeCN) and [Cu(TMG₂dmtrien)][Cl]₂ · 3MeCN ( C2 [Cl]₂ · 3MeCN). The cations C1 and C2 [Cu(TMG₂dmtrien)]²⁺ show a square‐planar coordination environment and are chiral with both enantiomers being observed in the unit cell. We investigated the application of L1 in copper‐mediated styrene ATRP. L1 shows with CuBr and PEBr as initiator a high polymerization activity according to the polymerization rate. First order kinetics confirm the living character of the polymerization. However, the deviation of molecular weights from theoretical molecular weights and the broad molecular weight distributions hint for a low controlled ATRP. The ATRP with further copper(I) salts {CuCl, [Cu(MeCN)₄]BF₄ and [Cu(MeCN)₄]PF₆} and PECl and PEBr as initiators were investigated as well. Herein the use of [Cu(MeCN)₄]PF₆ with PECl led to promising results.     

Size does matter! Label-free detection of small molecule–protein interaction

This review is focused on methods for detecting small molecules and, in particular, the characterisation of their interaction with natural proteins (e.g. receptors, ion channels). Because there are intrinsic advantages to using label-free methods over labelled methods (e.g. fluorescence, radioactivity), this review only covers label-free techniques. We briefly discuss available techniques and their advantages and disadvantages, especially as related to investigating the interaction between small molecules and proteins. The reviewed techniques include well-known and widely used standard analytical methods (e.g. HPLC-MS, NMR, calorimetry, and X-ray diffraction), newer and more specialised analytical methods (e.g. biosensors), biological systems (e.g. cell lines and animal models), and in-silico approaches.     

Nitrogen uptake of nickel free austenitic stainless steel powder during heat treatment—an XPS study

In austenitic stainless steel nitrogen stabilizes the austenitic phase, improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn‐prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X‐ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide‐free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.