Thermal and sensitiveness determination of cubanes: towards cubane‐based fuels for infrared countermeasures

As infrared seeking technology evolves, threats are better able to distinguish defensive infrared (IR) flares from true targets. Spectrally matched flares, which generally employ carbon-based fuels, are better able to decoy some advanced missiles by more closely mimicking the IR emission of the target. Cubane is a high-energy carbon-based scaffold which may be suitable for use as a fuel in spectrally matched flares. The enthalpy of formation and strain energy of a series of cubanes was predicted in silico, and their thermal and impact stability examined. All were found to undergo highly exothermic decomposition in sealed cell differential scanning calorimetry, and two cubanes subsequently underwent quantitative sensitiveness testing. Despite their F of I values being in the secondary explosive range, cubane-1,4-dicarboxylic acid (F of I=70) and 4-carbamoylcubane-1-carboxylic acid (F of I=90) were identified as potentially useful fuels for pyrotechnic infrared countermeasure flare formulations

Cubane, Bicyclo[1.1.1]pentane and Bicyclo[2.2.2]octane: Impact and Thermal Sensitiveness of Carboxyl-, Hydroxymethyl- and Iodo-substituents

With the burgeoning interest in cage motifs for bioactive molecule discovery, and the recent disclosure of 1,4-cubane-dicarboxylic acid impact sensitivity, more research into the safety profiles of cage scaffolds is required. Therefore, the impact sensitivity and thermal decomposition behavior of judiciously selected starting materials and synthetic intermediates of cubane, bicyclo[1.1.1]pentane (BCP), and bicyclo[2.2.2]octane (BCO) were evaluated via hammer test and sealed cell differential scanning calorimetry, respectively. Iodo-substituted systems were found to be more impact sensitive, whereas hydroxymethyl substitution led to more rapid thermodecomposition. Cubane was more likely to be impact sensitive with these substituents, followed by BCP, whereas all BCOs were unresponsive. The majority of derivatives were placed substantially above Yoshida thresholds-a computational indicator of sensitivity

Regular and complex singularities of the generalized thin film equation in two dimensions

We use a generalized version of the equation of motion for a thin film of liquid on a solid, horizontal substrate as a model system to study the formation of singularities in space dimensions greater than one. Varying both the exponent controlling long-ranged forces, as well as the exponent of the nonlinear mobility, we predict the structure of the singularity as the film thickness goes to zero. The spatial structure of rupture may be either 'pointlike' (approaching axisymmetry) or 'quasi-one-dimensional', in which case a one-dimensional singularity is unfolded into two or higher space dimensions. The scaling of the profile with time may be either strictly self-similar (the 'regular' case) or discretely self-similar and perhaps chaotic (the 'irregular' case). We calculate the phase boundaries between these regimes, and confirm our results by detailed comparisons with time-dependent simulations of the nonlinear thin film equation in two space dimensions.</p

Dichloro-naphthoquinone as a non-classical inhibitor of the mycobacterial carbonic anhydrase Rv3588c

The soluble mycobacterial carbonic anhydrases Rv3588c and Rv1284 belong to a different class of carbonic anhydrases than those found in humans, making them attractive drug targets by using the inherent differences in the folds of the different classes. By screening a natural product library, we identified naphthoquinone derivatives as a novel non-classical inhibitor scaffold of mycobacterial carbonic anhydrases that lack the sulfonamide/sulfamate group and thus did not affect human carbonic anhydrase II

On the Use of Differential Scanning Calorimetry for Thermal Hazard Assessment of New Chemistry: Avoiding Explosive Mistakes

Differential scanning calorimetry (DSC) is increasingly used as evidence to support a favourable safety profile of novel chemistry, or to highlight the need for caution. DSC enables preliminary assessment of the thermal hazards of a potentially energetic compound. However, unlike other standard characterisation methods, which have well defined formats for reporting data, the current reporting of DSC results for thermal hazard assessment has shown concerning trends. Around half of all results in 2019 did not include experimental details required to replicate the procedure. Furthermore, analysis for thermal hazard assessment is often only conducted in unsealed crucibles, which could lead to misleading results and dangerously incorrect conclusions. We highlight the specific issues with DSC analysis of hazardous compounds currently in the organic chemistry literature and provide simple ‘best practice’ guidelines which will give chemists confidence in reported DSC results and the conclusions drawn from them

A tunable high-pass filter for simple and inexpensive size-segregation of sub-10-nm nanoparticles

Recent advanced in the fields of nanotechnology and atmospheric sciences underline the increasing need for sizing sub-10-nm aerosol particles in a simple yet efficient way. In this article, we develop, experimentally test and model the performance of a High-Pass Electrical Mobility Filter (HP-EMF) that can be used for sizing nanoparticles suspended in gaseous media. Experimental measurements of the penetration of nanoparticles having diameters down to ca 1nm through the HP-EMF are compared with predictions by an analytic, a semi-empirical and a numerical model. The results show that the HPEMF effectively filters nanoparticles below a threshold diameter with an extremely high level of sizing performance, while it is easier to use compared to existing nanoparticle sizing techniques through design simplifications. What is more, the HP-EMF is an inexpensive and compact tool, making it an enabling technology for a variety of applications ranging from nanomaterial synthesis to distributed monitoring of atmospheric nanoparticles.ChemE/Materials for Energy Conversion & Storag

Ranking oxidant sensitiveness: a guide for synthetic utility

Common oxidants used in chemical synthesis, including newly developed perruthenates, were evaluated in the context of understanding (and better appreciating) the sensitiveness and associated potential hazards of these reagents. Analysis using sealed cell differential scanning calorimetry (scDSC) facilitated Yoshida correlations, which were compared to impact sensitiveness and electrostatic discharge experiments (ESD), that enabled sensitiveness ranking. Methyltriphenylphoshonium perruthenate (MTP3, 8), isoamyltriphenylphosphonium perruthenate (ATP3, 7) and tetraphenylphosphonium perruthenate (TP3, 9) were found to be the most sensitive followed by 2-iodoxybenzoic acid (IBX, 2) and benzoyl peroxide (BPO, 10), whereas the most benign were observed to be Oxone (12), manganese dioxide (MnO , 13), and N-bromosuccinimide (NBS, 17)