Azobenzene-containing triazatriangulenium adlayers on Au(111): structural and spectroscopic characterization

Adlayers of different azobenzene-functionalized derivatives of the triazatriangulenium (TATA) platform on Au(111) surfaces were studied by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), gap-mode surface-enhanced Raman spectroscopy (gap-mode SERS), and cyclic voltammetry (CV). The chemical composition of the adlayers is in good agreement with the molecular structure, i.e., different chemical groups attached to the azobenzene functionality were identified. Furthermore, the presence of the azobenzene moieties in the adlayers was verified by the vibration spectra and electrochemical data. These results indicate that the molecules remain intact upon adsorption with the freestanding functional groups oriented perpendicularly to the TATA platform and thus also to the substrate surface.     

Mechanism of the living lactide polymerization mediated by robust zinc guanidine complexes

Zinc bis(chelate) guanidine complexes promote living lactide polymerization at elevated temperatures. By means of kinetic and spectroscopic analyses the mechanism has been elucidated for these special initiators that make use of neutral N-donor ligands. The neutral guanidine function initiates the polymerization by a nucleophilic ring-opening attack on the lactide molecule. DFT calculations on the first ring-opening step show that the guanidine is able to act as a nucleophile. Three transition states were located for ligand rearrangement, nucleophilic attack, and ring-opening. The second ring-opening step was modeled as a representation for the chain growth because here, the lactate alcoholate opens the second lactide molecule via two transition states (nucleophilic attack and ring-opening). Additionally, the resulting reaction profile proceeds overall exothermically, which is the driving force for the reaction. The experimental and calculated data are in good agreement and the presented mechanism explains why the polymerization proceeds without co-initiators.     

Synthesis of 3-methoxyazetidines via an aziridine to azetidine rearrangement and theoretical rationalization of the reaction mechanism

The synthetic utility of N-alkylidene-(2,3-dibromo-2-methylpropyl)amines and N-(2,3-dibromo-2-methylpropylidene)benzylamines was demonstrated by the unexpected synthesis of 3-methoxy-3-methylazetidines upon treatment with sodium borohydride in methanol under reflux through a rare aziridine to azetidine rearrangement. These findings stand in contrast to the known reactivity of the closely related N-alkylidene-(2,3-dibromopropyl)amines, which are easily converted into 2-(bromomethyl)aziridines under the same reaction conditions. A thorough insight into the reaction mechanism was provided by both experimental study and theoretical rationalization.     

Inhibition of prefrontal protein synthesis following recall does not disrupt memory for trace fear conditioning

Background  

The extent of similarity between consolidation and reconsolidation is not yet fully understood. One of the differences noted is that not every brain region involved in consolidation exhibits reconsolidation. In trace fear conditioning, the hippocampus and the medial prefrontal cortex (mPFC) are required for consolidation of long-term memory. We have previously demonstrated that trace fear memory is susceptible to infusion of the protein synthesis inhibitor anisomycin into the hippocampus following recall. In the present study, we examine whether protein synthesis inhibition in the mPFC following recall similarly results in the observation of reconsolidation of trace fear memory.     

A Uniqueness Result for a Model for Mixtures in the Absence of External Forces and Interaction Momentum

We consider a continuum model describing steady flows of a miscible mixture of two fluids. The densities ϱ _i of the fluids and their velocity fields u ⁽ⁱ⁾ are prescribed at infinity: ϱ _i |_∞ = ϱ _i∞ > 0, u ⁽ⁱ⁾|∞ = 0. Neglecting the convective terms, we have proved earlier that weak solutions to such a reduced system exist. Here we establish a uniqueness type result: in the absence of the external forces and interaction terms, there is only one such solution, namely ϱ _i ≡ ϱ _i∞, u ⁽ⁱ⁾ ≡ 0, i = 1, 2. This work was supported by the SFB 611 at the University of Bonn and the European HYKE network (contract no. HPRN-CT-2002-00282). The third author was also supported by the project CSF 201/03/0934, and by MSM 0021620839.     

Heisenberg groups—A unifying structure of signal theory, holography and quantum information theory

Vector fields in three-space admit bundles of internal variables such as a Heisenberg algebra bundle. Information transmission along field lines of vector fields is described by a wave linked to the Schrödinger representation in the realm of time-frequency analysis. The preservation of local information causes geometric optics and a quantization scheme. A natural circle bundle models quantum information visualized by holographic methods. Features of this setting are applied to magnetic resonance imaging.