Cationic Aluminium Complexes as Catalysts for Imine Hydrogenation

Strongly Lewis acidic cationic aluminium complexes, stabilized by β–diketiminate (BDI) ligands and free of Lewis bases, have been prepared as their B(C₆F₅)₄⁻ salts and were investigated for catalytic activity in imine hydrogenation. The backbone (R1) and N (R2) substituents on the ^R1,R2BDI ligand (^R1,R2BDI=HC[C(R1)N(R2)]₂) influence sterics and Lewis acidity. Ligand bulk increases along the row ^Me,DIPPBDI<^Me,DIPePBDI≈^tBu,DIPPBDI<^tBu,DIPePBDI; DIPP=2,6-C(H)Me₂-phenyl, DIPeP=2,6-C(H)Et₂-phenyl. The Gutmann-Beckett test showed acceptor numbers of: (^tBu,DIPPBDI)AlMe⁺ 85.6, (^tBu,DIPePBDI)AlMe⁺ 85.9, (^Me,DIPPBDI)AlMe⁺ 89.7, (^Me,DIPePBDI)AlMe⁺ 90.8, (^Me,DIPPBDI)AlH⁺ 95.3. Steric and electronic factors need to be balanced for catalytic activity in imine hydrogenation. Open, highly Lewis acidic, cations strongly coordinate imine rendering it inactive as a Frustrated Lewis Pair (FLP). The bulkiest cations do not coordinate imine but its combination is also not an active catalyst. The cation (^tBu,DIPPBDI)AlMe⁺ shows the best catalytic activity for various imines and is also an active catalyst for the Tishchenko reaction of benzaldehyde to benzylbenzoate. DFT calculations on the mechanism of imine hydrogenation catalysed by cationic Al complexes reveal two interconnected catalytic cycles operating in concert. Hydrogen is activated either by FLP reactivity of an Al⋅⋅⋅imine couple or, after formation of significant quantities of amine, by reaction with an Al⋅⋅⋅amine couple. The latter autocatalytic Al⋅⋅⋅amine cycle is energetically favoured.     

Altered Membrane Mechanics Provides a Receptor-Independent Pathway for Serotonin Action

Serotonin, an important signaling molecule in humans, has an unexpectedly high lipid membrane affinity. The significance of this finding has evoked considerable speculation. Here we show that membrane binding by serotonin can directly modulate membrane properties and cellular function, providing an activity pathway completely independent of serotonin receptors. Atomic force microscopy shows that serotonin makes artificial lipid bilayers softer, and induces nucleation of liquid disordered domains inside the raft-like liquid-ordered domains. Solid-state NMR spectroscopy corroborates this data at the atomic level, revealing a homogeneous decrease in the order parameter of the lipid chains in the presence of serotonin. In the RN46A immortalized serotonergic neuronal cell line, extracellular serotonin enhances transferrin receptor endocytosis, even in the presence of broad-spectrum serotonin receptor and transporter inhibitors. Similarly, it increases the membrane binding and internalization of oligomeric peptides. Our results uncover a mode of serotonin–membrane interaction that can potentiate key cellular processes in a receptor-independent fashion.     

Refined Analysis of Sparse MIMO Radar

We analyze a multiple-input multiple-output (MIMO) radar model and provide recovery results for a compressed sensing (CS) approach. In MIMO radar different pulses are emitted by several transmitters and the echoes are recorded at several receiver nodes. Under reasonable assumptions the transformation from emitted pulses to the received echoes can approximately be regarded as linear. For the considered model, and many radar tasks in general, sparsity of targets within the considered angle-range-Doppler domain is a natural assumption. Therefore, it is possible to apply methods from CS in order to reconstruct the parameters of the targets. Assuming Gaussian random pulses the resulting measurement matrix becomes a highly structured random matrix. Our first main result provides an estimate for the well-known restricted isometry property (RIP) ensuring stable and robust recovery. We require more measurements than standard results from CS, like for example those for Gaussian random measurements. Nevertheless, we show that due to the special structure of the considered measurement matrix our RIP result is in fact optimal (up to possibly logarithmic factors). Our further two main results on nonuniform recovery (i.e., for a fixed sparse target scene) reveal how the fine structure of the support set—not only the size—affects the (nonuniform) recovery performance. We show that for certain “balanced” support sets reconstruction with essentially the optimal number of measurements is possible. Indeed, we introduce a parameter measuring the well-behavedness of the support set and resemble standard results from CS for near-optimal parameter choices. We prove recovery results for both perfect recovery of the support set in case of exactly sparse vectors and an \(\ell _2\)-norm approximation result for reconstruction under sparsity defect. Our analysis complements earlier work by Strohmer & Friedlander and deepens the understanding of the considered MIMO radar model. Thereby—and apparently for the first time in CS theory—we prove theoretical results in which the difference between nonuniform and uniform recovery consists of more than just logarithmic factors.     

Numerical investigation of the effective Skempton coefficient in fluid-saturated fractured rock

Characterization of hydro-mechanical processes in reservoir rocks is an essential issue for many geo investigations such as characterization of subsurface fluid flow or geothermal exploitation. For geothermal applications, the role of fractures as storage and transport components of a hydraulic system are highly important. In the present contribution we focus on investigating the effective Skempton coefficient of a damaged porous rock analyzing a modified Cryer problem, which provides a simple model of a porous rock containing a storage and transport pat. The effective Skempton coefficient is defined as the ratio of the increase in mean pore pressure induced by change in confining pressure for undrained boundary conditions. Using approaches from computational homogenization, we evaluate the confining pressure as the negative volume average of the total mean stress. Similarly, we compute the effective fluid pressure in terms of the volume-averaged fluid pressure in the rocks. We compare the numerical results to those from typical experiments and highlight the problems with the latter. The proposed concept for determination of an effective Skempton coefficient based on numerically evaluated volume averages helps to generate a better understanding of the process-inherent constituents. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dibora[2]ferrocenophane: A Carbene-Stabilized Diborene in a Strained cis-Configuration

Unsaturated bridges that link the two cyclopentadienyl ligands together in strained ansa metallocenes are rare and limited to carbon–carbon double bonds. The synthesis and isolation of a strained ferrocenophane containing an unsaturated two-boron bridge, isoelectronic with a C=C double bond, was achieved by reduction of a carbene-stabilized 1,1′-bis(dihaloboryl)ferrocene. A combination of spectroscopic and electrochemical measurements as well as density functional theory (DFT) calculations was used to assess the influence of the unprecedented strained cis configuration on the optical and electrochemical properties of the carbene-stabilized diborene unit. Initial reactivity studies show that the dibora[2]ferrocenophane is prone to boron–boron double bond cleavage reactions.     

Analysis of synaptic bodies in the Sprague-Dawley rat pineal gland under extreme photoperiods

Synaptic bodies (SBs) are small, prominent organelles in pinealocytes, most probably involved in signal transduction processes. To check the influence of the photoperiod on their shape plasticity and number we chose two extreme lighting conditions, i.e. 20h of illumination followed by 4h of darkness (LD 20:4) versus (LD 4:20). Pineal glands were assessed at 0, 4 and 13h after dark onset. Under both conditions reconstructed SBs were plates or ribbons but never spheres and there were no obvious differences in morphology. Photoperiodic changes in SB profile size and number were investigated: application of the established method for SB quantification based on single section profile counts (SSPC) of areas showed a significant increase of SB profiles under LD 20:4. However, it has to be noted that SSPC depend on both, number and size of the structures. In contrast to this, modification of the disector counting method, also applied for unbiased quantification of whole SBs, revealed that rat pinealocytes show insignificantly more SBs under LD 20:4 than under 4:20 conditions. The lengths of the SB profiles, which were first measured under different conditions in this study, depend on SB size. They increased significantly under LD 20:4. In conclusion, we detected only an increase in SB size but not in their number. We further prove that, at least for SBs, it is of no value to calculate disector levels from SSPCs.     

Open-shell singlet character of cyclacenes and short zigzag nanotubes

The electronic ground states of [n]cyclacenes, as well as short-zigzag nanotubes, computed at unrestricted broken spin-symmetry density functional theory (UBS-DFT), were found to be open-shell singlets, rather than triplets. Computations for [6]cyclacene at complete active space self-consistent field (CASSCF) and multireference perturbation theory (MRMP2) levels support this conclusion. Along with strain, the radical character of the open-shell singlet with antiferromagnetically coupled electron spins may contribute to the difficulties in synthesizing [n]cyclacenes.     

Stable photoinduced charge separation in heptacene

Heptacene, generated in inert gas matrices by photobisdecarbonylation of a bridged alpha-diketone precursor, undergoes ionization into radical anion and radical cation upon UV irradiation.