More Like this

1. Very thermostable energetic materials based on a fused-triazole: 3,6-diamino-1 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole

   https://doi.org/10.1039/d0nj05152g  

   Tang, Yongxing; An, Ziwei; Chinnam, Ajay Kumar; Staples, Richard J.; Shreeve, Jean'ne M. (January 2021, New Journal of Chemistry)

   null (Ed.)

   3,6-Diamino-1 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole ( 1 ) and its energetic salts ( 2–9 ) were designed and synthesized based on a fused-triazole backbone with two C-amino groups as substituents. Their physicochemical and energetic properties were measured or calculated. Among them, compound 1 exhibits superior thermostability ( T d (onset) : 261 °C), surpassing its analogues 3,7-diamino-7 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole (DATT, 219 °C) and 3,6,7-triamino-7 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole (TATOT, 245 °C). The differences in thermal stabilities were further investigated by determining the lowest bond dissociation energies (BDE) where a positive correlation between the stability of the molecules and the lowest BDE values is observed. The results show that 1 with the highest value for the lowest BDE has a superior thermostability in comparison to DATT and TATOT. The energetic salts ( 2–9 ) also exhibit remarkable thermal stabilities as well as low impact and friction sensitivities. The fused-triazole backbone 1 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazole with two C-amino groups as substituents is shown to be a promising building block for construction of very thermally stable energetic materials. 

   more » « less
2. Bridged and fused triazolic energetic frameworks with an azo building block towards thermally stable and applicable propellant ingredients

   https://doi.org/10.1039/d1ta07520a  

   Yu, Qiong; Li, Fengsheng; Yin, Ping; Pang, Siping; Staples, Richard J.; Shreeve, Jean'ne M. (November 2021, Journal of Materials Chemistry A)

   The assembly of nitrogen-rich building blocks determines the energy storage capacity and affects the stability of energetic materials. Owing to the environmentally harmful properties of the propellant, ammonium perchlorate (AP), much research has explored halogen-free replacements which often suffer from poor thermal stability. In our goal of balancing performance and stability, we report access to an energetic molecule (3) by smart assembly of an azo bridge into trinitromethyl triazoles. Compound 3 exhibits a decomposition temperature of 175 °C, which approaches the highest among reported trinitromethyl derivatives. The density (1.91 g cm −3 ) and oxygen balance (+29%) for 3 exceed other candidates, suggesting it as a high energy dense oxidizer (HEDO) replacement for AP in rocket propellants. One-step azo-involved cyclization of 3 give two fused nitro triazolones, (FNTO) 4 and its N -oxide 5, having thermal stabilities and energies superior to the analogous derivatives of 5-nitro-2,4-dihydro-3 H -1,2,4-triazole-3-one (NTO). The comparison of properties of the fused triazolones 4 and 8 and their N -oxide derivatives 5 and 9 shows that formation of an N -oxide is an effective strategy which results in an increase of the decomposition temperature, oxygen balance, specific impulse, and detonation properties and in a decrease of the sensitivity of the corresponding energetic material. This work highlights bridged and fused triazolic energetic frameworks with an azo building block providing an alternative structural motif for seeking an applicable high-energy ingredient. 

   more » « less
3. SET activation of nitroarenes by 2-azaallyl anions as a straightforward access to 2,5-dihydro-1,2,4-oxadiazoles

   https://doi.org/10.1038/s41467-021-26767-x  

   Zou, Dong; Gan, Lishe; Yang, Fan; Wang, Huan; Pu, Youge; Li, Jie; Walsh, Patrick J. (December 2021, Nature Communications)

   Abstract The use of nitroarenes as amino sources in synthesis is challenging. Herein is reported an unusual, straightforward, and transition metal-free method for the net [3 + 2]-cycloaddition reaction of 2-azaallyl anions with nitroarenes. The products of this reaction are diverse 2,5-dihydro-1,2,4-oxadiazoles (>40 examples, up to 95% yield). This method does not require an external reductant to reduce nitroarenes, nor does it employ nitrosoarenes, which are often used in N–O cycloadditions. Instead, it is proposed that the 2-azaallyl anions, which behave as super electron donors (SEDs), deliver an electron to the nitroarene to generate a nitroarene radical anion. A downstream 2-azaallyl radical coupling with a newly formed nitrosoarene is followed by ring closure to afford the observed products. This proposed reaction pathway is supported by computational studies and experimental evidence. Overall, this method uses readily available materials, is green, and exhibits a broad scope. 

   more » « less
4. Stimulation of ammonia oxidizer and denitrifier abundances by nitrogen loading: Poor predictability for increased soil N ₂ O emission

   https://doi.org/10.1111/gcb.16042  

   Zhang, Yong; Zhang, Feng; Abalos, Diego; Luo, Yiqi; Hui, Dafeng; Hungate, Bruce A.; García‐Palacios, Pablo; Kuzyakov, Yakov; Olesen, Jørgen Eivind; Jørgensen, Uffe; et al (December 2021, Global Change Biology)

   Abstract Unprecedented nitrogen (N) inputs into terrestrial ecosystems have profoundly altered soil N cycling. Ammonia oxidizers and denitrifiers are the main producers of nitrous oxide (N₂O), but it remains unclear how ammonia oxidizer and denitrifier abundances will respond to N loading and whether their responses can predict N‐induced changes in soil N₂O emission. By synthesizing 101 field studies worldwide, we showed that N loading significantly increased ammonia oxidizer abundance by 107% and denitrifier abundance by 45%. The increases in both ammonia oxidizer and denitrifier abundances were primarily explained by N loading form, and more specifically, organic N loading had stronger effects on their abundances than mineral N loading. Nitrogen loading increased soil N₂O emission by 261%, whereas there was no clear relationship between changes in soil N₂O emission and shifts in ammonia oxidizer and denitrifier abundances. Our field‐based results challenge the laboratory‐based hypothesis that increased ammonia oxidizer and denitrifier abundances by N loading would directly cause higher soil N₂O emission. Instead, key abiotic factors (mean annual precipitation, soil pH, soil C:N ratio, and ecosystem type) explained N‐induced changes in soil N₂O emission. Altogether, these findings highlight the need for considering the roles of key abiotic factors in regulating soil N transformations under N loading to better understand the microbially mediated soil N₂O emission. 

   more » « less
5. Instability growth rates in hydrofluorocarbon/air flames: analysis of the Rayleigh-Taylor instability

   Tavares, Justin K; Jayachandran, Jagannath (March 2024, Spring Techical Meeting of the Eastern States Section of the Combustion Institute)

   Hydrofluorocarbons (HFC), which are mildly flammable and pose potential fire risks, have received greater attention as a viable low global warming potential alternative to traditional refrigerant and fire-suppressant compounds. However, the reactivity of these compounds can be exacerbated under certain conditions, with buoyancy-induced instability growth promoting flame acceleration and substantially increasing flame speeds of HFC/oxidizer deflagrations. Therefore, the flame acceleration of HFC/oxidizer deflagrations must be investigated to properly assess the flammability characteristics of these compounds. This study investigates the effect of the Rayleigh-Taylor instability on instability growth rates during the linear regime. To this end, simulations were performed tracking the growth of instabilities caused by an initial disturbance in the flame front, from which dispersion relations were derived for R-32/air mixtures varying the gravitational acceleration. 

   more » « less