Synthesis of Highly Functionalized N,N-Diarylamides by an Anodic C,N-Coupling Reaction

We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways.     

Kinetics and mechanism of trichloroisocyanuric acid/NaNO2-triggered nitration of aromatic compounds under acid-free and Vilsmeier-Haack conditions

Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO₂, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO₂, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO₂ under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO₂]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO₂), 365.8 K (TCCA-DMF)/NaNO₂, and 358 K (TCCA-DMA)/NaNO₂. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction.     

Seeded Polymerization of an Amide-Functionalized Diketopyrrolopyrrole Dye in Aqueous Media

The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the presence of water molecules due to hydration. This conformational change is most likely responsible for the trapping of monomers in the initial stage of the cooperative supramolecular polymerization in aqueous media. However, the monomeric species can selectively interact with externally added fragmented aggregates as seeds through concerted π-stacking and hydrogen-bonding interactions. Consequently, the time course of the supramolecular polymerization and the morphology of the aggregated state can be controlled, and one-dimensional fibers that exhibit a J-aggregate-like bathochromically shifted absorption band can be obtained.     

Experimental determination of interfacial energy for solid Al in the Al-Sn-Mg eutectic system with Bridgman-type apparatus

The equilibrated grain boundary groove shape of solid Al in equilibrium with Al-Sn-Mg eutectic liquid was observed by using a Bridgman type directional solidification apparatus. The ratio of the thermal conductivity of the equilibrated liquid to the thermal conductivity of solid Al has been obtained as 0.91. In addition, the average Gibbs-Thomson coefficient, $\bar{\mathrm{\Gamma }}=(4.20\pm 0.35)\times {10}^{-8}\mathrm{Km}$, the solid-liquid interfacial energy, ${\sigma }_{SL}=180.68\pm 23.48\text{mJ}/{\text{m}}^2$ and the grain boundary energy, ${\sigma }_{GB}=309.30\pm 29.47\text{mJ}/{\text{m}}^2$, in the Al/Al-Sn-Mg system have been calculated from the measured grain boundary shapes.     

Acoustic phonon impact on the inter-Coulombic decay process in charged quantum dot pairs

ABSTRACT

Recently, highly accurate multi-configuration time-dependent Hartree electron dynamics calculations demonstrated the efficient long-range energy transfer inter-Coulombic decay (ICD) process to happen in charged semiconductor quantum dot (QD) pairs. ICD is initiated by intraband photoexcitation of one of the QDs and leads to electron emission from the other within a duration of about 150 ps. On the same time scale electronically excited states are reported to relax due to the coupling of electrons to acoustic phonons. Likewise, phonons promote ionisation. Here, the QDs' acoustic breathing mode is implemented in a frozen-phonon approach. A detailed comparison of the phonon effects on electron relaxation and emission as well as on the full ICD process is presented, which supports the previous empirical finding of ICD being the dominant decay channel in paired QDs. In addition the relative importance of phonon–phonon, phonon–electron and electron–electron interaction is analysed.     

Compressibility of random walker trajectories on growing networks

We find that the simple coupling of network growth to the position of a random walker on the network generates a traveling wave in the probability distribution of nodes visited by the walker. We argue that the entropy of this probability distribution is bounded as the network size tends to infinity. This means that the growth of a space coupled to a random walker situated in it constrains its dynamics to a set of typical random walker trajectories, and walker trajectories inside the growing space are compressible.     

Shape morphing and topology optimization of fluid channels by explicit boundary tracking

An integrated shape morphing and topology optimization approach based on the deformable simplicial complex methodology is developed to address Stokes and Navier‐Stokes flow problems. The optimized geometry is interpreted by a set of piecewise linear curves embedded in a well‐formed triangular mesh, resulting in a physically well‐defined interface between fluid and impermeable regions. The shape evolution is realized by deforming the curves while maintaining a high‐quality mesh through adaption of the mesh near the structural boundary, rather than performing global remeshing. Topological changes are allowed through hole merging or splitting of islands. The finite element discretization used provides smooth and stable optimized boundaries for simple energy dissipation objectives. However, for more advanced problems, boundary oscillations are observed due to conflicts between the objective function and the minimum length scale imposed by the meshing algorithm. A surface regularization scheme is introduced to circumvent this issue, which is specifically tailored for the deformable simplicial complex approach. In contrast to other filter‐based regularization techniques, the scheme does not introduce additional control variables, and at the same time, it is based on a rigorous sensitivity analysis. Several numerical examples are presented to demonstrate the applicability of the approach.