Predictive model for ice formation on superhydrophobic surfaces

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies.     

The co-ordination chemistry of tris(3,5-dimethylpyrazolyl)methane manganese carbonyl complexes: synthetic, electrochemical and DFT studies

The tricarbonyl [Mn(CO)(3){HC(pz')(3)}][PF(6)] 1(+)[PF(6)](-) (pz' = 3,5-dimethylpyrazolyl) reacts with a range of P-, N- and C-donor ligands, L, in the presence of trimethylamine oxide to give [Mn(CO)(2)L{HC(pz')(3)}](+) {L = PEt(3)3(+), P(OEt)(3)4(+), P(OCH(2))(3)CEt 5(+), py 6(+), MeCN 7(+), CNBu(t)8(+) and CNXyl 9(+)}. The complex [Mn(CO)(2)(PMe(3)){HC(pz')(3)}](+)2(+) is formed by reaction of 7(+) with PMe(3). Complexes 2(+) and 6(+) were structurally characterised by X-ray diffraction methods. Reaction of 7(+) with half a molar equivalent of 4,4'-bipyridine gives a purple compound assumed to be the bridged dimer [{HC(pz')(3)}Mn(CO)(2)(μ-4,4'-bipy)Mn(CO)(2){HC(pz')(3)}](2+)10(2+). The relative electron donating ability of HC(pz')(3) has been established by comparison with the cyclopentadienyl and tris(pyrazolyl)borate analogues. Cyclic voltammetry shows that each of the complexes undergoes an irreversible oxidation. The correlation between the average carbonyl stretching frequency and the oxidation potential for complexes of P- and C-donor ligands is coincident with the correlation observed for [Mn(CO)(3-m)L(m)(η-C(5)H(5-n)Me(n))]. The data for complexes of N-donor ligands, however, are not coincident due to the presence of a node (and phase change) between the metal and the N-donor in the HOMO of the complex as suggested by preliminary DFT calculations.     

Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles

The stereospecific 1,2‐migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2‐migration of boronate complexes is driven by displacement of an α‐leaving group, oxidation of an α‐boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile‐induced stereospecific 1,2‐migration of groups from boron to sp² and sp³ carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2‐migration of boronate complexes: stereospecific Zweifel‐type reactions, catalytic conjunctive coupling reactions, and transition metal‐free sp²–sp³ couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.     

Modulation versus Templating: Fine‐Tuning of Hierarchally Porous PCN‐250 Using Fatty Acids To Engineer Guest Adsorption

Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal–organic frameworks (HP‐MOFs). In this study, by using fatty acids with different lengths and concentrations as dual‐functional modulators/templates, we were able to obtain HP‐MOFs with tunable mesopores that exhibit different pore diameters and locations. We found that the length and concentration of the fatty acids can determine if micelle formation occurs, which in turn dictates the porosity of the resulting HP‐MOFs. The HP‐MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure–performance relationships were ascribed to the pore diameters and locations. This approach could provide a potentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.     

Self-assembly of a thymine quartet and quadruplex via an organic template

The synthesis of two hydrophobic cavitands bearing four (1) and eight (2) thymidine residues covalently linked with triazole moieties is reported. Spectral evidence indicates the adoption of a hydrogen-bonded T-quartet assembly by 1 in chloroform at low temperature and a π-stacked quadruplex by 2 in DMSO under ambient conditions.     

Traveling wave magnetophoresis for high resolution chip based separations

A new mode of magnetophoresis is described that is capable of separating micron-sized superparamagnetic beads from complex mixtures with high sensitivity to their size and magnetic moment. This separation technique employs a translating periodic potential energy landscape to transport magnetic beads horizontally across a substrate. The potential energy landscape is created by superimposing an external, rotating magnetic field on top of the local fixed magnetic field distribution near a periodic arrangement of micro-magnets. At low driving frequencies of the external field rotation, the beads become locked into the potential energy landscape and move at the same velocity as the traveling magnetic field wave. At frequencies above a critical threshold, defined by the bead's hydrodynamic drag and magnetic moment, the motion of a specific population of magnetic beads becomes uncoupled from the potential energy landscape and its magnetophoretic mobility is dramatically reduced. By exploiting this frequency dependence, highly efficient separation of magnetic beads has been achieved, based on fractional differences in bead diameter and/or their specific attachment to two microorganisms, i.e., B. globigii and S. cerevisiae.     

How Carbon Nanotube Crushing can Improve Flame Retardant Behaviour in Polymer Nanocomposites?

Nanocomposites based on an ethylene–vinyl acetate copolymer (27 wt.‐% vinyl acetate) and multiwall carbon nanotubes (MWNTs) have been prepared by melt blending and their thermal degradation and flame retardant properties have been evaluated. Special attention has been paid to the influence of the nanotube nature on the flammability properties and more particularly on the time to ignition (TTI) as measured by cone calorimetry. It has been shown that there is a strong influence of the nature of carbon nanotubes on the fire behaviour of the composites, especially previous MWNTs crushing proved to substantially delay the TTI while maintaining much reduced heat release rate (HRR). Such a remarkable behaviour might be explained by the chemical reactivity of radical species present at the surface/extremities of crushed MWNTs during the combustion process.

     

Thermally Rearranged Polymer Membranes Containing Tröger's Base Units Have Exceptional Performance for Air Separations

The influence of segmental chain motion on the gas separation performance of thermally rearranged (TR) polymer membranes is established for TR polybenzoxazoles featuring Tröger's base (TB) monomer subunits as exceptionally rigid sites of contortion along the polymer backbone. These polymers are accessed from solution‐processable ortho‐acetate functionalized polyimides, which are readily synthesized as high‐molecular‐weight polymers for membrane casting. We find that thermal rearrangement leads to a small increase in d‐spacing between polymer chains and a dramatic pore‐network reconfiguration that increases both membrane permeability and O₂/N₂ selectivity, putting its performance above the 2015 upper bound.