Solvent-free dehydration, cyclization, and hydrogenation of linalool with a dual heterogeneous catalyst system to generate a high-performance sustainable aviation fuel.

The development of efficient catalytic methods for the synthesis of bio-based, full-performance jet fuels is critical for limiting the impacts of climate change while enabling a thriving modern society. To help address this need, here, linalool, a terpene alcohol that can be produced via fermentation of biomass sugars, was dehydrated, cyclized, and hydrogenated in a one-pot reaction under moderate reaction conditions. This sequence produced a biosynthetic fuel mixture primarily composed of 1-methyl-4-isopropylcyclohexane (p-menthane) and 2,6-dimethyloctane (DMO). The reaction was promoted by a catalyst composed of commercial Amberlyst-15, H+ form, and 10% Pd/C. Two other terpenoid substrates (1,8-cineole and 1,4-cineole) were subjected to the same conditions and excellent conversion to high purity p-menthane was observed. The fuel mixture derived from linalool exhibits a 1.7% higher gravimetric heat of combustion and 66% lower kinematic viscosity at -20 °C compared to the limits for conventional jet fuel. These properties suggest that isomerized hydrogenated linalool (IHL) can be blended with conventional jet fuel or synthetic paraffinic kerosenes to deliver high-performance sustainable aviation fuels for commercial and military applications.

Accelerated synthesis of energetic precursor cage compounds using confined volume systems.

Confined volume systems, such as microdroplets, Leidenfrost droplets, or thin films, can accelerate chemical reactions. Acceleration occurs due to the evaporation of solvent, the increase in reactant concentration, and the higher surface-to-volume ratios amongst other phenomena. Performing reactions in confined volume systems derived from mass spectrometry ionization sources or Leidenfrost droplets allows for reaction conditions to be changed quickly for rapid screening in a time efficient and cost-saving manner. Compared to solution phase reactions, confined volume systems also reduce waste by screening reaction conditions in smaller volumes prior to scaling. Herein, the condensation of glyoxal with benzylamine (BA) to form hexabenzylhexaazaisowurtzitane (HBIW), an intermediate to the highly desired energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), was explored. Five confined volume systems were compared to evaluate which technique was ideal for forming this complex cage structure. Substituted amines were also explored as BA replacements to screen alternative cage structure intermediates and evaluate how these accelerated techniques could apply to novel reactions, discover alternative reagents to form the cage compound, and improve synthetic routes for the preparation of CL-20. Ultimately, reaction acceleration is ideal for predicting the success of novel reactions prior to scaling up and determining if the expected products form, all while saving time and reducing costs. Acceleration factors and conversion ratios for each reaction were assessed by comparing the amount of product formed to the traditional bulk solution phase synthesis.

Rapid, in situ detection of chemical warfare agent simulants and hydrolysis products in bulk soils by low-cost 3D-printed cone spray ionization mass spectrometry.

Chemical warfare agents (CWAs) are toxic chemicals that have been used as disabling or lethal weapons in war, terrorist attacks, and assasinations. The Chemical Weapons Convention (CWC) has prohibited the use, development, production, and stockpiling of CWAs since its initiation in 1997, however, the threat of deployment still looms. Detection of trace CWAs post-deployment or post-remediation, in bulk matrices such as soil, often requires lengthy sample preparation steps or extensive chromatographic separation times. 3D-printed cone spray ionization (3D-PCSI), an ambient ionization mass spectrometric (MS) technique, provides a rapid, simple, and low-cost method for trace CWA analysis in soil matrices for both in-laboratory and in-field detection. Described here is the utilization of conductive 3D-printed cones to perform both rapid sampling and ionization for CWA simulants and hydrolysis products in eight solid matrices. The analysis of trace quantities of CWA simulants and hydrolysis products by 3D-PCSI-MS coupled to both a commercial benchtop system and a field-portable MS system is detailed. Empirical limits of detection (LOD) for CWA simulants on the benchtop MS ranged from 100 ppt to 750 ppb and were highly dependant on solid matrix composition, with the portable system yielding similar spectral data from alike matrices, albeit with lower sensitivity.