Infrared spectra of the complexes of trifluoroethene with dimethyl ether, acetone, and oxirane: a cryosolution study

Infrared spectra of solutions of trifluoroethene and dimethyl ether, acetone, or oxirane in liquid krypton and liquid argon have been studied. For each Lewis base the formation of a 1:1 complex with the Lewis acid was observed. The C-H stretching of trifluoroethene being perturbed by a strong Fermi resonance, the complexes with trifuloroethene-d were also investigated and showed that in each case the hydrogen bond between the acid and base is of the traditional, red-shifting type. The structures of the complexes were investigated using ab initio calculations. These indicate that with dimethyl ether and acetone two different isomeres can be formed, but with a single one detected in the solution in each case. The Fermi resonance in the complex with unlabeled trifluoroethene is discussed using data derived form ab initio potential and dipole hypersurface calculations. The complexation enthalpies of the complexes were obtained from temperature dependent studies of the solutions and are discussed in relation to the ab initio complexation energies and Monte Carlo free energy perturbation calculations of solvent effects.     

Odd-numbered oxacalix[n]arenes (n = 5, 7): synthesis and solid-state structures

The critical synthetic access to odd-numbered calix[n]arenes has evidently resulted in less attention for these macrocycles, although specific molecular recognition phenomena have been observed for some of them. A straightforward fragment coupling approach has been designed, applying kinetically controlled nucleophilic aromatic substitution reaction conditions, affording odd-numbered oxacalix[n]arenes (n = 5, 7) selectively in high yields. The solid-state conformational behavior and the oxacalix[n]arene cavity size were explored by single-crystal X-ray diffraction studies.     

Synthesis and characterization of water-soluble poly(p-phenylene vinylene) derivatives via the dithiocarbamate precursor route

Two hydrophilic branched oligo(ethylene glycol)-substituted PPV derivatives, poly(2,5-bis(1,3-bis(triethoxymethoxy)propan-2-yloxy)-1,4-phenylene vinylene) (BTEMP-PPV) and poly(2-methoxy-5-(1,3-bis(triethoxymethoxy)propan-2-yloxy)-1,4-phenylene vinylene) (MTEMP-PPV), are presented. Polymerizations have been performed via the dithiocarbamate precursor route, using lithium hexamethyldisilazide (LHMDS) as a base, to obtain high molecular weight precursor polymers. After thermal conversion of the precursor polymers into the fully conjugated systems, the solubility of the polymers has been examined. The polar nonionic side chains of MTEMP-PPV and BTEMP-PPV render the PPV backbone soluble in a variety of solvents, including alcohols and even water, making these polymers suitable candidates to be used in optoelectronic devices that can be processed from environmentally friendly solvent systems.     

A probability-mapping algorithm for calibrating the posterior probabilities: A direct marketing application

Calibration refers to the adjustment of the posterior probabilities output by a classification algorithm towards the true prior probability distribution of the target classes. This adjustment is necessary to account for the difference in prior distributions between the training set and the test set. This article proposes a new calibration method, called the probability-mapping approach. Two types of mapping are proposed: linear and non-linear probability mapping. These new calibration techniques are applied to 9 real-life direct marketing datasets. The newly-proposed techniques are compared with the original, non-calibrated posterior probabilities and the adjusted posterior probabilities obtained using the rescaling algorithm of Saerens et al. (2002). The results recommend that marketing researchers must calibrate the posterior probabilities obtained from the classifier. Moreover, it is shown that using a ‘simple’ rescaling algorithm is not a first and workable solution, because the results suggest applying the newly-proposed non-linear probability-mapping approach for best calibration performance.     

Homothiacalix[4]arenes: synthetic exploration and solid-state structures

Homothiacalix[n]arenes have been largely underexposed compared with related (homo)heteracalixarenes, although their inherent structural features are particularly attractive for supramolecular host-guest chemistry. In this contribution, the synthetic macrocyclization protocols that afford homothiacalix[n]arenes have been reinvestigated and optimized, providing straightforward access to the parent homothiacalix[4]arene skeleton. Moreover, inner-rim (bis and tetrakis) ester functionalization and dimethylenethia bridge oxidation were successfully performed as well. Solution-phase (variable-temperature) NMR spectroscopy studies and solid-state X-ray structures provided complementary information on the conformational features of the novel macrocycles.     

Neutral nickel oligo- and polymerization catalysts: the importance of alkyl phosphine intermediates in chain termination

An unconventional chain termination reaction has been explored for the SHOP (Shell higher olefin process)-type, anilinotropone, and salicylaldiminato nickel-based oligo- and polymerization catalysts by using density functional theory (DFT). Starting from the tetracoordinate alkyl phosphine complex, the termination reaction was found to involve a rearrangement of the alkyl chain to form a pentacoordinate β-agostic complex, β-hydride elimination, and olefinic chain dissociation and to compete with propagation at sufficiently high phosphine concentration and/or basicity. It provides the first complete and convincing mechanistic rationale for the decreasing chain lengths observed upon increasing phosphine concentration and basicity. The unconventional reaction was found to be a major termination pathway for the SHOP-type catalyst and is very unlikely to lead to branching and olefin isomerization, which is critical for explaining why the SHOP catalyst, in contrast to the anilinotropone and salicylaldiminato catalysts, tends to lead to the oligomerization of ethylene to form linear α-olefins. Based on our results we have proposed a new and extended catalytic cycle for the SHOP-type ethylene oligomerization catalyst. Finally, the importance of the new termination reaction for the SHOP-type catalyst suggests that this reaction may also operate with other ethylene oligomerization nickel catalysts. This prediction was confirmed for a pyrazolonatophosphine catalyst, for which the new termination route was found to be even more facile, which explains the short oligomers produced by this catalyst.     

Organic light‐emitting transistors with voltage‐tunable lit area and full channel illumination

Organic light‐emitting transistors (OLETs) are multifunctional optoelectronic devices that hold great promise for a variety of applications, including flat panel displays, integrated light sources for sensing and optical communication systems. The narrow illumination area within the device channel is considered intrinsic to the device architecture and is a severe technological drawback for all those applications where a controlled, wide and homogeneous emission area is required. Here it is shown that not only the position but also the extension of the emission area is voltage‐tunable, and the entire channel of the transistor can be homogeneously illuminated. The modeling of the exciton distribution within the channel at the different bias conditions coupled to the modeling of the device emission profile highlights that excitons are spread through the entire channel width and across the bulk of the central emission layer of the p‐channel/emitter/n‐channel trilayer active heterostructure.     

Increasing Preservation Efficiency and Product Quality through Control of Temperature Distributions in High Pressure Applications

The effectiveness of HP sterilisation is a function of both temperature and pressure. As during pressurisation the product temperature increases, heat transfer to the colder HPP vessel wall occurs and the product fraction near the vessel wall will be colder than the product in the middle of the vessel. The effect of the temperature distribution in the vessel on the inactivation of Bacillus stearothermophilus has been examined. A mathematical model has been built, in which both thermodynamics and inactivation kinetics are integrated. Heat transfer is based on a Finite Element simulation, inactivation kinetics are based on first order kinetics. Based on this model and experiments the effect of an homogeneous temperature distribution on inactivation is demonstrated.     

Crosslinked Polyvinylnorbornene‐Based Membranes as a New Class of Solvent‐Resistant Nanofiltration Membranes

Solvent resistant nanofiltration (SRNF) has received increasing attention since the turn of the century within energy‐ and waste‐efficient unit processes. This work explores the synthesis and characterization of crosslinked polynorbornenes for SRNF. A series of polyvinylnorbornene thin‐film composite membranes with increasing degree of crosslinking were prepared and tested for their SRNF performance in heptane, chloroform, and toluene. Sudan Black B (457 g mol^?1) was used as the solute. Then, 99% retention was achieved in heptane, 86% in chloroform, and 75% in toluene. It was further shown that the permeance and retention can be fine‐tuned in these solvents by controlling the extent of crosslinking. This work thus introduces the crosslinking of polynorbornenes as a promising material route for SRNF. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1593–1600