Dynamic Supramolecular Polymers Based on Benzene‐1,3,5‐tricarboxamides: The Influence of Amide Connectivity on Aggregate Stability and Amplification of Chirality

N‐Centred benzene‐1,3,5‐tricarboxamides (N‐BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid‐state behaviour and self‐assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X‐ray diffraction revealed that the chiral N‐BTA derivatives with branched 3,7‐dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Col_ho. In contrast, N‐BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable‐temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N‐BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N‐BTAs revealed a cooperative self‐assembly behaviour of the N‐BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants‐and‐soldiers as well as the majority‐rules principles were operative in stacks of N‐BTAs. In fact, the self‐assembly of N‐BTAs resembles closely that of their carbonyl (C?O)‐centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self‐assembly of N‐ and C?O‐BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N‐BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the Ph? NH bond compared to the Ph? CO bond and the diminished magnitude of dipole–dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N‐BTAs and C?O BTAs.     

Pulsed power corona discharges for air pollution control

Successful introduction of pulsed corona for industrial purposes very much depends on the reliability of high-voltage and pulsed power technology and on the efficiency of energy transfer. In addition, it is of the utmost importance that adequate electromagnetic compatibility (EMC) is achieved between the high-voltage pulse source and the surrounding equipment. Pulsed corona is generated in a pilot unit that produces narrow 50 MW pulses at 1000 pps (net average corona power 1.5 kW). The pilot unit can run continuously for use in industrial applications such as cleaning of gases (100 m³/h) containing NO or volatile organic compounds (VOCs) or fluids (e.g., waste water). Simultaneous removal of NO and ethylene to obtain clean CO₂ from the exhaust of a combustion engine was tested at an industrial site. Various chemical processes, such as removal of toluene or styrene from an airflow are tested in the laboratory. We developed a model to analyze the conversion of these pollutants. To examine the discharges in the reactor we use current, voltage, and E-field sensors as well as a fast charge-coupled device (CCD) camera. Detailed energy input measurements are compared with CCD movies to investigate the efficiency of different streamer phases. EMC techniques incorporated in the pilot unit are based on the successful concept of constructing a low transfer impedance between common mode currents induced by pulsed power and differential mode voltages in signal lines and external main lines     

Quantification of Stereochemical Communication in Metal–Organic Assemblies

The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per “incorrect” amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra‐ and inter‐vertex coupling constants are used to track the degree of stereochemical communication across a range of metal–organic assemblies (employing different ligands, peripheral amines, and metals); temperature‐dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal–organic container molecules.     

Spiral coils for counter-current chromatography using aqueous polymer two-phase systems

Retention properties of polyethylene glycol-phosphate aqueous two-phase systems in a spiral coil (5 mm I.D.) on Type-J synchronous counter-current chromatographic devices have been compared for the elution mode where the lower phase is the mobile phase and flows from the inside head terminal. This was achieved with the aid of digital imaging under stroboscopic illumination, an image analysis and measurement of the displaced volume of the stationary phase. For the spiral coil, high and stable stationary phase retention at mobile phase flow rates up to 64 ml/min has been obtained. Wave-like disturbance of the interface near the proximal point was observed and analyses have been made for possible use in protein separation.     

Tuning material properties of covalent adaptable networks containing boronate-TetraAzaADamantane bonds through systematic variation in electron density of ring substituents

An outstanding challenge in modern society remains how to make crosslinked polymers (thermosets) more recyclable. A breakthrough solution to this challenge has been the introduction of dynamic covalent bonds in polymer networks, yielding covalent adaptable networks (CANs). Ongoing research is focused on finding new suitable dynamic covalent chemistries and on how to tune the material properties of CANs derived from these new chemistries. Here, we first compare two different dynamic boronic acid based covalent adaptable networks, namely, a conventional boronate-diol and a novel boronate-TetraAzaADamantane (TAAD) system. We show that incorporating boronate-TAAD bonds in networks results in stiffer materials, as seen in a slower relaxation and higher shear and storage moduli. This offers access to more mechanically robust boronate-based materials, compared to conventional boronate-based gels. Next, we investigate the effect of molecular tuning via the electron density of meta-positioned ring substituents on the macroscopic material properties for the boronate-TAAD network. By comparing relaxation experiments on materials with different substituents, we show that the macroscopic network relaxation can be tuned through the Hammett parameter of the meta-substituent and the activation energy of the boronate-TAAD exchange. This enables subtle control over the (dynamic) material properties of these novel, robust boronate-based networks.     

Thermodynamics of supramolecular naphthalenediimide nanotube formation: the influence of solvents, side chains, and guest templates

Amino-acid functionalized naphthalenediimides self-assemble into hydrogen-bonded supramolecular helical nanotubes via a noncooperative, isodesmic process; the self-assembly of ordered helical systems is usually realized through a cooperative process. This unexpected behavior was rationalized as a manifestation of entropy-enthalpy compensation. Fundamental insights into the thermodynamics governing this self-assembly were obtained through the fitting of the isodesmic model to (1)H NMR spectrometry and circular dichroism spectroscopy measurements. Furthermore, we have extended the application of this mathematical model, for the first time, to quantitatively estimate the effect of guests, solvents, and side chains on the stability of the supramolecular nanotube; most significantly, we demonstrate that C(60) acts as a template to stabilize the nanotube assembly and thereby substantially increase the degree of polymerization.