Cu‐Based Catalyst Resulting from a Cu,Zn,Al Hydrotalcite‐Like Compound: A Microstructural,Thermoanalytical, and In Situ XAS Study

A Cu‐based methanol synthesis catalyst was obtained from a phase pure Cu,Zn,Al hydrotalcite‐like precursor, which was prepared by co‐precipitation. This sample was intrinsically more active than a conventionally prepared Cu/ZnO/Al₂O₃ catalyst. Upon thermal decomposition in air, the [(Cu_0.5Zn_0.17Al_0.33)(OH)₂(CO₃)_0.17] ? mH₂O precursor is transferred into a carbonate‐modified, amorphous mixed oxide. The calcined catalyst can be described as well‐dispersed “CuO” within ZnAl₂O₄ still containing stabilizing carbonate with a strong interaction of Cu²⁺ ions with the Zn–Al matrix. The reduction of this material was carefully analyzed by complementary temperature‐programmed reduction (TPR) and near‐edge X‐ray absorption fine structure (NEXAFS) measurements. The results fully describe the reduction mechanism with a kinetic model that can be used to predict the oxidation state of Cu at given reduction conditions. The reaction proceeds in two steps through a kinetically stabilized Cu^I intermediate. With reduction, a nanostructured catalyst evolves with metallic Cu particles dispersed in a ZnAl₂O₄ spinel‐like matrix. Due to the strong interaction of Cu and the oxide matrix, the small Cu particles (7 nm) of this catalyst are partially embedded leading to lower absolute activity in comparison with a catalyst comprised of less‐embedded particles. Interestingly, the exposed Cu surface area exhibits a superior intrinsic activity, which is related to a positive effect of the interface contact of Cu and its surroundings.     

Regioselective Hydroarylation Reactions of C3 Electrophilic N‐Acetylindoles Activated by FeCl3: An Entry to 3‐(Hetero)arylindolines

A method for the direct and rare umpolung of the 3 position of indoles is reported. The activation of N‐acetylindole with iron(III) chloride allows the C?H addition of aromatic and heteroaromatic substrates to the C2?C3 double bond of the indole nucleus to generate a quaternary center at C3 and leads regioselectively to 3‐arylindolines. Optimization, scope (50 examples), practicability (gram scale, air atmosphere, room temperature), and mechanistic insights of this process are presented. Synthetic transformations of the indoline products into drug‐like compounds are also described.     

Deciphering the structure of isomeric oligosaccharides in a complex mixture by tandem mass spectrometry: Photon activation with vacuum ultra-violet brings unique information and enables definitive structure assignment

Carbohydrates have a wide variety of structures whose complexity and heterogeneity challenge the field of analytical chemistry. Tandem mass spectrometry, with its remarkable sensitivity and high information content, provides key advantages to addressing the structural elucidation of polysaccharides. Yet, classical fragmentation by collision-activated dissociation (CAD) in many cases fails to reach a comprehensive structural determination, especially when isomers have to be differentiated. In this work, for the first time, vacuum ultra-violet (VUV) synchrotron radiation is used as the activation process in tandem mass spectrometry of large oligosaccharides. Compared to low energy CAD (LE-CAD), photon activated dissociation brought more straightforward and valuable structural information. The outstanding feature was that complete series of informative ions were produced, with only minor neutral losses. Moreover, systematic fragmentation rules could be drawn thus facilitating the definitive assignments of fragment identities. As a result, most of the structures present in a complex mixture of oligogalacturonans could be comprehensively resolved, including many isomers differing in the position of methyl groups along the galacturonic acid backbone.     

Effect of the Metal on Disulfide/Thiolate Interconversion: Manganese versus Cobalt

It has recently been proposed that disulfide/thiolate interconversion supported by transition‐metal ions is involved in several relevant biological processes. In this context, the present contribution represents a unique investigation of the effect of the coordinated metal (M) on the Mⁿ⁺?disulfide/M⁽ⁿ⁺¹⁾⁺?thiolate switch properties. Like its isostructural Co^II‐based parent compound, Co^II ₂ SS (Angew. Chem. Int. Ed.­ 2014 , 53, 5318), the new dinuclear disulfide‐bridged Mn^II complex Mn^II ₂ SS can undergo an M^II?disulfide/M^III?thiolate interconversion, which leads to the first disulfide/thiolate switch based on Mn. The coordination of iodide to the metal ion stabilizes the oxidized form, as the disulfide is reduced to the thiolate. The reverse process, which involves the reduction of M^III to M^II with the concomitant oxidation of the thiolates, requires the release of iodide. The Mn^II ₂ SS complex slowly reacts with Bu₄NI in CH₂Cl₂ to afford the mononuclear Mn^III?thiolate complex Mn^IIII . The process is much slower (ca. 16 h) and much less efficient (ca. 30 % yield) with respect to the instantaneous and quantitative conversion of Co^II ₂ SS into Co^IIII under similar conditions. This distinctive behavior can be rationalized by considering the different electrochemical properties of the involved Co and Mn complexes and the DFT‐calculated driving force of the disulfide/thiolate conversion. For both Mn and Co systems, M^II?disulfide/M^III?thiolate interconversion is reversible. However, when the iodide is removed with Ag⁺, the M^II ₂ SS complexes are regenerated, albeit much slower for Mn than for Co systems.     

Analysis of the turbulent boundary layer in the vicinity of a self-excited cylindrical Helmholtz resonator

This study investigates the changes in the structure of a turbulent boundary layer downstream of a flow-excited Helmholtz resonator. To this end, a fully developed turbulent boundary layer over a resonator mounted flush with a flat plate was simulated by implementing a large eddy simulation (LES). To assist in understanding the effect of the resonator on the flow structure, a sensitivity study was undertaken by changing the main geometrical parameters of the resonator. The results demonstrated that when the boundary layer thickness equals the orifice length, the cross-stream component of velocity fluctuations penetrates the boundary layer, resulting in a reduction of the turbulence intensity by up to 12%. Therefore, it is concluded that a Helmholtz resonator has the potential to reduce the instabilities within the boundary layer. These investigations also assist in identifying the optimal parameters to delay turbulence events within the grazing flow using Helmholtz resonators.     

Ueber einige Pflanzengifte

Ohne Zusammenfassung     

An equivalence between varieties of cyclic Post algebras and varieties generated by a finite field

In this paper we give a term equivalence between the simple k-cyclic Post algebra of order p, L _p,k, and the finite field F(p ^k) with constants F(p). By using Lagrange polynomials, we give an explicit procedure to obtain an interpretation Φ₁ of the variety V(L _p,k) generated by L _p,k into the variety V(F(p ^k)) generated by F(p ^k) and an interpretation Φ₂ of V(F(p ^k)) into V(L _p,k) such that Φ₂Φ₁(B) = B for every B ε V(L _p,k) and Φ₁Φ₂(R) = R for every R ε V(F(p ^k)).     

Mass Determination of Entire Amyloid Fibrils by Using Mass Spectrometry

Amyloid fibrils are self‐assembled protein structures with important roles in biology (either pathogenic or physiological), and are attracting increasing interest in nanotechnology. However, because of their high aspect ratio and the presence of some polymorphism, that is, the possibility to adopt various structures, their characterization is challenging and basic information such as their mass is unknown. Here we show that charge‐detection mass spectrometry, recently developed for large self‐assembled systems such as viruses, provides such information in a straightforward manner.     

Excited States of Xanthene Analogues: Photofragmentation and Calculations by CC2 and Time‐Dependent Density Functional Theory

Action spectroscopy has emerged as an analytical tool to probe excited states in the gas phase. Although comparison of gas‐phase absorption properties with quantum‐chemical calculations is, in principle, straightforward, popular methods often fail to describe many molecules of interest—such as xanthene analogues. We, therefore, face their nano‐ and picosecond laser‐induced photofragmentation with excited‐state computations by using the CC2 method and time‐dependent density functional theory (TDDFT). Whereas the extracted absorption maxima agree with CC2 predictions, the TDDFT excitation energies are blueshifted. Lowering the amount of Hartree–Fock exchange in the DFT functional can reduce this shift but at the cost of changing the nature of the excited state. Additional bandwidth observed in the photofragmentation spectra is rationalized in terms of multiphoton processes. Observed fragmentation from higher‐lying excited states conforms to intense excited‐to‐excited state transitions calculated with CC2. The CC2 method is thus suitable for the comparison with photofragmentation in xanthene analogues.