From Surface‐Inspired Oxovanadium Silsesquioxane Models to Active Catalysts for the Oxidation of Alcohols with O2—The Cinnamic Acid/Metavanadate System

Silsesquioxane dioxovanadate(V) complexes were investigated with respect to their potential as a catalyst for the oxidative dehydrogenation of alcohols with O₂ as an oxidant. The turnover frequencies determined were comparatively low, but during the oxidation of cinnamic alcohol an increase in activity was observed in the course of the process, which was inspected more closely. It turned out that during the oxidation of cinnamic alcohol, not only was the aldehyde formed but also cinnamic acid, which in turn reacts with the silsesquioxane complex employed to give NBu₄[O₂V(O₂CC₂H₂Ph)₂], which can also be obtained from NBu₄VO₃ and cinnamic acid and represents a far more active catalyst, not only for cinnamic alcohol but also for other activated alcohols and hydrocarbons. The rate‐determining step of the conversion corresponds to an hydrogen‐atom abstraction from the C? H units, as shown by the determination of the kinetic isotope effect in case of 9‐hydroxyfluorene, and the reoxidation of the reduced catalyst proceeds via a peroxo intermediate, which is also capable of oxidizing one alcohol equivalent. Furthermore the influence of the organic residues at the carboxylate ligands on the catalyst performance was investigated, which showed that the activity increases with decreasing pK_s value. Moreover, it was found that during the oxidation the catalyst slowly decomposes, but can be regenerated by addition of excessive carboxylic acid.     

The Complexed 1,3‐Diphospha‐2‐Arsaallyl Radical and Its Cationic and Anionic Derivatives

Photolysis of [Cp*As{W(CO)₅}₂] ( 1 a ) in the presence of Mes*P?PMes* (Mes*=2,4,6‐tri‐tert‐butylphenyl) leads to the novel 1,3‐diphospha‐2‐arsaallyl radical [(CO)₅W(μ,η²:η¹‐P₂AsMes*₂)W(CO)₄] ( 2 a ). The frontier orbitals of the radical 2 a are indicative of a stable π‐allylic system that is only marginally influenced by the d orbitals of the two tungsten atoms. The SOMO and the corresponding spin density distribution of the radical 2 a show that the unpaired electron is preferentially located at the two equivalent terminal phosphorus atoms, which has been confirmed by EPR spectroscopy. The protonated derivative of 2 a , the complex [(CO)₅W(μ,η²:η¹‐P₂As(H)Mes*₂)W(CO)₄] ( 6 a ) is formed during chromatographic workup, whereas the additional products [Mes*P?PMes*{W(CO)₅}] as the Z‐isomer ( 3 ) and the E‐isomer ( 4 ), and [As₂{W(CO)₅}₃] ( 5 ) are produced as a result of a decomposition reaction of radical 2 a . Reduction of radical 2 a yields the stable anion [(CO)₅W(μ,η²:η¹‐P₂AsMes*₂)W(CO)₄]^? in 7 a , whereas upon oxidation the corresponding cationic complex [(CO)₅W(μ,η²:η¹‐P₂AsMes*₂)W(CO)₄][SbF₆] ( 8 a ) is formed, which is only stable at low temperatures in solution. Compounds 2 a , 7 a , and 8 a represent the hitherto elusive complexed redox congeners of the diphospha‐arsa‐allyl system. The analogous oxidation of the triphosphaallyl radical [(CO)₅W(μ,η²:η¹‐ P₃Mes*₂)W(CO)₄] ( 2 b ) also leads to an allyl cation, which decomposes under CH activation to the phosphine derivative [(CO)₅W{μ,η²:η¹‐P₃(Mes*)(C₅H₂tBu₂C(CH₃)₂CH₂)}W(CO)₄] ( 9 ), in which a CH bond of a methyl group of the Mes* substituent has been activated. All new products have been characterized by NMR spectrometry and IR spectroscopy, and compounds 2 a , 3 , 6 a , 7 a , and 9 by X‐ray diffraction analysis.     

DMA analysis and wood bonding of PVAc latex reinforced with cellulose nanofibrils

Suspensions of commercial refined beech pulp (RBP) were further processed through mechanical disintegration (MD-RBP), chemical modification (CM-RBP) and through chemical modification followed by mechanical disintegration (CM-MD-RBP). Nanocomposites were prepared by compounding a poly(vinyl acetate) (PVAc) latex adhesive with increasing contents of the different types of nanofibrils, and the resulting nanocomposites were analyzed by dynamic mechanical analysis (DMA). Also, the suitability of using the CM-RBP fibrils to formulate PVAc adhesives for wood bonded assemblies with improved heat resistance was studied. The presence of cellulose nanofibrils had a strong influence on the viscoelastic properties of PVAc latex films. For all nanocomposites, increasing amounts of cellulose nanofibrils (treated or untreated) led to increasing reinforcing effects in the glassy state, but especially in the PVAc and PVOH glass transitions. This reinforcement primarily resulted from interactions between the cellulose fibrils network and the hydrophilic PVOH matrix that led to the complete disappearance of the PVOH glass transition (tan δ peak) for some fibril types and contents. At any given concentration in the PVOH transition, the CM-MD-RBP nanofibrils provided the highest reinforcement, followed by the MD-RBP, CM-RBP and the untreated RBP. Finally, the use of the CM-RBP fibrils to prepare PVAc reinforced adhesives for wood bonding was promising since, even though they generally performed worse in dry and wet conditions, the boards showed superior heat resistance (EN 14257) and passed the test for durability class D1.     

Werkzeug für die Chemische Biologie. Semisynthese

Semisynthetic techniques have greatly contributed to the rapid development of Chemical Biology in recent years. In this regard the semisynthesis of complex modified proteins as well as the selective derivatization of natural products has evolved into more than mere proof‐of‐principle concepts but powerful tools to probe protein functions. This technology provides a solid basis for further investigations on proteomics and qualitative and quantitative cell biology. The interdisciplinary charter bridging chemistry and biology is the hallmark of semisynthesis. It can be expected that its scientific impact will further increase in the future.     

Semisynthese. Chemie mit den Molekülen der Natur

In Semisynthesis complex molecules have to be manipulated in a chemoselective, regioselective, and stereoselective fashion, necessitating smart protective group operations and innovative synthesis development. Key are always easily accessible and suitable starting materials, especially intermediates which can be produced by biotechnological processes. An extensive synthetic construction of drug candidates carries high innovative and intellectual property protection potential, hence multistep semi‐ and even total syntheses are an integral part of modern industrial research and drug development. Not a long time ago, the complexity such realized would have been inconceivable, which profoundly illustrates the progress synthesis methodology has made. Semisynthesis always aims more toward focussed application, and hence its scientific contribution mostly cater to the elucidation of molecular correlations. Especially the study of cellular processes and their quantification will be stimulated in the future. Thereby semisynthesis will continue to bridge the key future areas of synthesis research and chemical biology.     

Quinol-containing ligands enable high superoxide dismutase activity by modulating coordination number,charge, oxidation states and stability of manganese complexes throughout redox cycling

Reactivity assays previously suggested that two quinol-containing MRI contrast agent sensors for H₂O₂, [Mn(H2qp1)(MeCN)]²⁺ and [Mn(H4qp2)Br₂], could also catalytically degrade superoxide. Subsequently, [Zn(H2qp1)(OTf)]⁺ was found to use the redox activity of the H2qp1 ligand to catalyze the conversion of O₂˙⁻ to O₂ and H₂O₂, raising the possibility that the organic ligand, rather than the metal, could serve as the redox partner for O₂˙⁻ in the manganese chemistry. Here, we use stopped-flow kinetics and cryospray-ionization mass spectrometry (CSI-MS) analysis of the direct reactions between the manganese-containing contrast agents and O₂˙⁻ to confirm the activity and elucidate the catalytic mechanism. The obtained data are consistent with the operation of multiple parallel catalytic cycles, with both the quinol groups and manganese cycling through different oxidation states during the reactions with superoxide. The choice of ligand impacts the overall charges of the intermediates and allows us to visualize complementary sets of intermediates within the catalytic cycles using CSI-MS. With the diquinolic H4qp2, we detect Mn(iii)-superoxo intermediates with both reduced and oxidized forms of the ligand, a Mn(iii)-hydroperoxo compound, and what is formally a Mn(iv)-oxo species with the monoquinolate/mono-para-quinone form of H4qp2. With the monoquinolic H2qp1, we observe a Mn(ii)-superoxo ↔ Mn(iii)-peroxo intermediate with the oxidized para-quinone form of the ligand. The observation of these species suggests inner-sphere mechanisms for O₂˙⁻ oxidation and reduction that include both the ligand and manganese as redox partners. The higher positive charges of the complexes with the reduced and oxidized forms of H2qp1 compared to those with related forms of H4qp2 result in higher catalytic activity (k_cat ∼ 10⁸ M⁻¹ s⁻¹ at pH 7.4) that rivals those of the most active superoxide dismutase (SOD) mimics. The manganese complex with H2qp1 is markedly more stable in water than other highly active non-porphyrin-based and even some Mn(ii) porphyrin-based SOD mimics.

Manganese complexes with polydentate quinol-containing ligands are found to catalyze the degradation of superoxide through inner-sphere mechanisms. The redox activity of the ligand stabilizes higher-valent manganese species.     

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

A new solvatomorph of [Au₃(1-Methylimidazolate)₃] (Au₃(MeIm)₃)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au₃(MeIm)₃ has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.     

Determination of phase transition points of ionic liquids by combination of thermal analysis and conductivity measurements at very low heating and cooling rates

The determination of phase transition points of nine different ionic liquids (ILs) was performed by thermal analysis with simultaneous recording of conductivity. Conductivity of electrolyte solutions and ILs drastically changes during phase transitions and thus is an additional and very sensitive indicator for measuring phase transition points. Evaluation of temperature–time functions and conductivity–time functions with our computer-coupled automated equipment enabled the determination of melting temperatures with high accuracy and reliability. This claim is based on large samples, low temperature change rates and by regularly repeated measurements, i.e. at least seven measurements per IL. The melting temperatures of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium tris(penta-fluoroethyl)trifluorophosphate, and 1-methyl-3-propylimidazolium iodide were, to our knowledge, determined for the first time. The melting temperatures of the other 1-butyl-1-methylpyrrolidinium-, 1-ethyl-3-methylimidazolium-, 1-hexyl-3-methylimidazolium-, and trimethylsulfonium-based ILs showed either a very good accordance with values published in literature or were distinctly higher.     

On decomposing mixed-mode oscillations and their return maps

Alternating patterns of small and large amplitude oscillations occur in a wide variety of physical, chemical, biological, and engineering systems. These mixed-mode oscillations (MMOs) are often found in systems with multiple time scales. Previous differential equation modeling and analysis of MMOs have mainly focused on local mechanisms to explain the small oscillations. Numerical continuation studies reported different MMO patterns based on parameter variation. This paper aims at improving the link between local analysis and numerical simulation. Our starting point is a numerical study of a singular return map for the Koper model which is a prototypical example for MMOs, which also relates to local normal form theory. We demonstrate that many MMO patterns can be understood geometrically by approximating the singular maps with affine and quadratic maps. Motivated by our numerical analysis we use abstract affine and quadratic return map models in combination with two local normal forms that generate small oscillations. Using this decomposition approach we can reproduce many classical MMO patterns and effectively decouple bifurcation parameters for local and global parts of the flow. The overall strategy we employ provides an alternative technique for understanding MMOs.     

The dynamic range of useful temporal fine structure cues for speech in the presence of a competing talker

Within an auditory channel, the speech waveform contains both temporal envelope (E(O)) and temporal fine structure (TFS) information. Vocoder processing extracts a modified version of the temporal envelope (E') within each channel and uses it to modulate a channel carrier. The resulting signal, E'(Carr), has reduced information content compared to the original "E(O)?+ TFS" signal. The dynamic range over which listeners make additional use of E(O)?+ TFS over E'(Carr) cues was investigated in a competing-speech task. The target-and-background mixture was processed using a 30-channel vocoder. In each channel, E(O)?+ TFS replaced E'(Carr) at either the peaks or the valleys of the signal. The replacement decision was based on comparing the short-term channel level to a parametrically varied "switching threshold," expressed relative to the long-term channel level. Intelligibility was measured as a function of switching threshold, carrier type, target-to-background ratio, and replacement method. Scores showed a dependence on all four parameters. Derived intensity-importance functions (IIFs) showed that E(O)?+ TFS information from 8-13 dB below to 10 dB above the channel long-term level was important. When E(O)?+ TFS information was added at the peaks, IIFs peaked around -2 dB, but when E(O)?+ TFS information was added at the valleys, the peaks lay around +1 dB.