High-energy Compounds Research Articles

Optimization of the key steps of synthesis and study of the fundamental physicochemical properties of high energy compounds — 4-(2,2,2-trinitroethyl)-2,6,8,10,12-pentanitrohexaazaisowurtzitane and 4,10-bis(2,2,2-trinitroethyl)-2,6,8,12-tetranitrohexaazaisowurtzitane

The key steps of the synthesis of two high energy compounds, namely, 4-(2,2,2-trinitroethyl)-2,6,8,10,12-pentanitrohexaazaisowurtzitane and 4,10-bis(2,2,2-trinitroethyl)-2,6,8,12-tetranitrohexaazaisowurtzitane, were optimized. Their enthalpy of formation, density, impact and friction sensitivity, and thermal stability were experimentally determined.

Synthesis, structure, and characterization of high-energy 4,6-diazido-N-(4,6-diazido-1,3,5-triazin-2-yl)-1,3,5-triazin-2-amine

The high-energy compound 4,6-diazido-N-(4,6-diazido-1,3,5-triazin-2-yl)-1,3,5-triazin-2-amine was obtained in high yield by azidation of 4,6-dichloro-N-(4,6-dichloro-1,3,5-triazin-2-yl)-1,3,5-triazin-2-amine with sodium azide in acetone. According to 13С and 15N NMR spectral data, the obtained tetraazide did not undergo azido-tetrazole tautomerism in DMSO solutions and existed solely in the azide form. This tetraazide formed a molecular 1:1 complex with pyridine, the structure of which was confirmed by X-ray structural analysis. The obtained tetraazide had an exceptionally high melting point among azidotriazines (220–222°С), high enthalpy of formation (1641 kJ/mol) and may be of interest as starting compound for the preparation of new high-energy materials.

Synthesis of N-(1-methyltetrazol-5-yl)trinitroacetimidamide

The reaction of 3-methyl-5-trinitromethyltetrazolо[1,5-а][1, 3, 5]triazin-7-one with water led to the opening of 1,3,5-triazine ring and preservation of trinitromethyl group in the product. The obtained N-(1-methyltetrazol-5-yl)trinitroacetimidamide is of interest as highenergy compound.

Comparative theoretical studies of differently bridged nitramino-substituted ditetrazole 2-N-oxides with high detonation performance and an oxygen balance of around zero.

In this work, six (A-F) nitramino (-NHNO2)-substituted ditetrazole 2-N-oxides with different bridging groups (-CH2-, -CH2-CH2-, -NH-, -N=N-, and -NH-NH-) were designed. The six compounds were based on the parent compound tetrazole 2-N-oxide, which possesses a high oxygen balance and high density. The structure, heat of formation, density, detonation properties (detonation velocity D and detonation pressure P), and the sensitivity of each compound was investigated systematically via density functional theory, by studying the electrostatic potential, and using molecular mechanics. The results showed that compounds A-F all have outstanding energetic properties (D: 9.1-10.0km/s; P: 38.0-46.7GPa) and acceptable sensitivities (h 50: 28-37cm). The bridging group present was found to greatly affect the detonation performance of each ditetrazole 2-N-oxide, and the compound with the -NH-NH- bridging group yielded the best results. Indeed, this compound (F) was calculated to have comparable sensitivity to the famous and widely used high explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), but with values of D and P that were about 8.7% and 19.4% higher than those for HMX, respectively. The present study shows that tetrazole 2-N-oxide is a useful parent compound which could potentially be used in the design of new and improved high-energy compounds to replace existing energetic compounds such as HMX.

Polymer with pendant diazo-coupling functionality for colorimetric detection of nitrates

Most high-energy compounds contain nitrates. Visual onsite nitrate and nitrite ion detection is, therefore, important for security related issues. Visual also has applications in environmental and biomedical sciences. These ions are colorimetrically detected by diazo coupling reaction between N-(1-naphthyl)ethylenediamine and sulfanilamide (known as the Griess reagent). We report on the synthesis of a polymer with N-(1-naphthyl)ethylenediamine and sulfanilamide side chains (mimicking the Griess reagent). The polymer matrix was further doped with zinc powder that reduces the nitrate ions to nitrite, thus initiating a diazotization reaction. The resultant diazo-coupled product produces a visually distinguishable color change to low nitrate concentration (∼4ppm).

Nitrato Functionalized Polymers for High Energy Propellants and Explosives: Recent Advances

Future propellants and explosive research focus on developing compositions with less vulnerability without compromising performance. This has provided impetus for research in the area of high energy materials and compounds free from pollution, for safe handling, high performance, reliability and reproducibility. The energetic oxidizers and energetic binders are being developed in this scenario for use in composite propellants and explosives. In a propellant, the binder holds together the matrix containing solid oxidizer particles and finely divided metal particles. It provides structural integrity and aid the combustion of the propellant. Any new development in this area wherein the binder can contribute to the energetic is of immense importance. This can be achieved by incorporation of energetic groups such as nitrato (−ONO2), azide (−N3) or flurodinitro CF(NO2)2 as side chain or on to the existing polymer backbone. Among these, nitrato functionalized energetic binders can find application in myriad areas like boosters, plastic bonded explosives, gas generators and pyrogen igniters. The present article is a concise review on various types of nitrato binders; their synthesis, properties and their propellant studies. Copyright © 2017 John Wiley & Sons, Ltd.

DFT study on the effect of relative positions of methyl-, nitro- and N→oxide groups on the molecular structure, thermal/kinetic stability, crystal density, heat of decomposition and performance characteristics of triazolones

ABSTRACTMethyl-, nitro- and N→oxide substituted triazolones are of interest in the contest of high-energy density compounds and have been found to have true local energy minima at the B3LYP/aug-cc-pVDZ level. The optimised structures, harmonic frequencies and thermodynamic values for all the model molecules have been obtained in their ground state. The velocity of detonation (D) and detonation pressure (P) have been evaluated by the Kamlet–Jacob equations using the crystal density and the heat of explosion. The estimated performance properties are higher (D = 9.92–10.27 km/s, P = 48.10–52.52 GPa) compared with 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (D = 9.20 km/s, P = 42.0 Gpa). The higher densities are possibly due to the intramolecular hydrogen bonds and the layered structures in the crystal lattice. We speculate that the calculated heat of explosion and the density are for the gas phase compounds and in the reality they should be for the solid phase which would diminish the magnitude of the calculated values. The –N→O and –NO2 group leads to the desirable consequences of higher heat of explosion and diminished sensitivities. The substituting of N–H hydrogen atom(s) of triazolones for a –CH3 group decreases melting point, heat of formation and density; however, the methyl group increases the thermal stability.

SYNTHESIS, STRUCTURE, AND CHARACTERIZATION OF HIGH-ENERGY 4,6-DIAZIDO- N -(4,6-DIAZIDO-1,3,5-TRIAZIN-2-YL)-1,3,5-TRIAZIN-2-AMINE

The high-energy compound 4,6-diazido- N -(4,6-diazido-1,3,5-triazin-2-yl)-1,3,5-triazin-2-amine was obtained in high yield by azidation of 4,6-dichloro- N -(4,6-dichloro-1,3,5-triazin-2-yl)-1,3,5-triazin-2-amine with sodium azide in acetone. According to 13 С and 15 N NMR spectral data, the obtained tetraazide did not undergo azido-tetrazole tautomerism in DMSO solutions and existed solely in the azide form. This tetraazide formed a molecular 1:1 complex with pyridine, the structure of which was confirmed by X-ray structural analysis. The obtained tetraazide had an exceptionally high melting point among azidotriazines (220–222°С), high enthalpy of formation (1641 kJ/mol) and may be of interest as starting compound for the preparation of new high-energy materials. Authors: Sergei V. Chapyshev*, Denis V. Korchagin

Oxygen exchange and energy metabolism in erythrocytes of Rett syndrome and their relationships with respiratory alterations.

Rett syndrome (RTT) is a neurodevelopmental disorder, mainly affecting females, which is associated to a mutation on the methyl-CpG-binding protein 2 gene. In the pathogenesis and progression of classic RTT, red blood cell (RBC) morphology has been shown to be an important biosensor for redox imbalance and chronic hypoxemia. Here we have evaluated the impact of oxidation and redox imbalance on several functional properties of RTT erythrocytes. In particular, we report for the first time a stopped-flow measurement of the kinetics of oxygen release by RBCs and the analysis of the intrinsic affinity of the hemoglobin (Hb). According to our experimental approach, RBCs from RTT patients do not show any intrinsic difference with respect to those from healthy controls neither in Hb's oxygen-binding affinity nor in O2 exchange processes at 37°C. Therefore, these factors do not contribute to the observed alteration of the respiratory function in RTT patients. Moreover, the energy metabolism of RBCs, from both RTT patients and controls, was evaluated by ion-pairing HPLC method and related to the level of malondialdehyde and to the oxidative radical scavenging capacity of red cells. Results have clearly confirmed significant alterations in antioxidant defense capability, adding important informations concerning the high-energy compound levels in RBCs of RTT subjects, underlying possible correlations with inflammatory tissue alterations.

Effect of storage and temperature on two biochemical analytes (creatinine and urea) in pooled serum samples stored at -20°C

Introduction: Creatinine and urea are nonprotein nitrogenous compounds which are eliminated from the body. Creatinine is a word obtained from a Greek term Kreas meaning flesh. An anhydrous form of creatine is creatinine. Around 0.5% of total muscle weight constitutes creatine. Muscle, brain, blood, etc., are the tissues, in which creatinine is present as high-energy compound, phosphocreatine, and creatine as free compound. Optimal storage of serum specimens in biobanks for long time for multicenter reference interval studies remains to be determined. Hence, in this context, the present study was undertaken to determine the effect of storage time and temperature on the laboratory results of urea and creatinine in pooled serum samples. Objective: To determine the effect of storage and temperature on two biochemical analytes (creatinine and urea) in pooled serum samples stored at ­20°C. Materials and Methods: The study comprised ten pooled serum samples. Each pooled serum sample was prepared by mixing ten individual serum samples. The serum samples were used for the estimation of effect of storage and temperature on two biochemical analytes (creatinine and urea) in pooled serum samples stored at ­20°C in semi-automated analyzer by kit method. Results: The results of the present study on creatinine concentration were found to increase above the normal levels in ten pooled serum samples after storage for 10 days at ­20°C. Concentration of urea was found to increase above the normal levels (>20-40 mg/dL) in two samples out of ten, whereas other eight samples were found to be within the normal range. Conclusion: The levels of creatinine were affected due to storage at ­20°C for 10 days. However, urea retained its stability when stored at ­20°C for 10 days. Thus, to ensure valid results, the samples should be analyzed within 24 h of collection.

金属錯体と半導体を複合化した光触媒および光電気化学セルによるCO<sub>2</sub>還元反応

Reduction of CO2 producing high-energy compounds using water as an electron donor and sun light as an energy source has been investigating as useful technology for solving both depletion of the fossil resources and the global warming problem. Our group has successfully developed several types of hybrid photocatalysts consisting of semiconductors and metal complexes, which have both efficient CO2 reduction ability supplied by the metal-complex unit and strong oxidation power of semiconductors. In this paper, our recent progresses of the visible-light-driven hybrid photocatalytic and photoelectrochemical systems for CO2 reduction are introduced: (1) hybrids consisting C3N4 and Ru(II) mononuclear complexes, (2) semiconductors, e.g., TaON, and a Ru(II)-Ru’(II) binuclear complex, (3) a photoelectrochemical cell comprising a photocathode of the Ru(II)-Re(I) binuclear complex immobilized on p-type semiconductor NiO and a CoOx/TaON photoanode. First two systems can photocatalyze CO2 reduction using methanol as an electron donor, and the third photoelectrochemical system can reduce CO2 using water as a reductant.

New Strategy That Delays Progression of Amyotrophic Lateral Sclerosis in G1H-G93A Transgenic Mice: Oral Administration of Xanthine Oxidoreductase Inhibitors That Are Not Substrates for the Purine Salvage Pathway

Amyotrophic lateral sclerosis (ALS), Lou Gehrig's disease, is a progressive fatal neurodegenerative disease that involves both upper and lower motor neurons. We orally administered 4 xanthine oxidoreductase (XOR) inhibitors to G1H-G93A mice carrying 25 transgene copy numbers of human mutant G93A superoxide dismutase 1, from 80 days of age. Three nonpurine-analogue inhibitors (TEI-6720: Febuxostat, Y-700 and FYX-051), but not allopurinol with a purine analogue ring (pyrazolo pyrimidine ring), significantly delayed disease onset, prolonged survival and the duration of disease stages, improved clinical signs, and alleviated weight loss. Exercise testing (extension reflex, inclined plane, footprint, rotarod, and beam balance tests) showed significantly improved motor function in the G1H-G93A mice treated with these 3 inhibitors. Significant amelioration of disease was seen even when TEI-6720 or Y-700 was administered after the appearance of early signs. Histopathological evaluation in the late stage revealed that G1H-G93A mice treated with TEI-6720 had well-preserved motor neurons and fewer inclusion bodies, compared with mice treated with placebo or with allopurinol. Our results indicate that these 3 nonpurine-analogue XOR inhibitors might increase the supply of high-energy compounds via the purine salvage pathway, thereby protecting motor neurons against death. This strategy may be applicable for oral therapy of ALS patients.

Catalyst: Chemistry’s Role in Providing Clean and Affordable Energy for All

Image Leif Hammarstrom is a professor of chemical physics at Uppsala University, Sweden. He is one of the leaders of the Swedish Consortium for Artificial Photosynthesis, founded in the mid-1990s. He is chair of the Swedish Solar Energy Platform and represents Uppsala University as a core member of the Solar Fuels Institute.

The plant lipidome in human and environmental health.

Lipids and oils derived from plant and algal photosynthesis constitute much of human daily caloric intake and provide the basis for high-energy bioproducts, chemical feedstocks for countless applications, and even fossil fuels over geological time scales. Sustainable production of high-energy compounds from plants is essential to preserving fossil fuel sources and ensuring the well-being of future generations. As a result of progress in basic research on plant and algal lipid metabolism, in combination with advances in synthetic biology, we can now tailor plant lipids for desirable biological, physical, and chemical properties. We highlight recent advances in plant lipid translational biology and discuss untapped areas of research that might expand the application of plant lipids.

Theoretical design of bicyclo[2.2.1]heptane derivatives for high-energy density compounds with low impact sensitivity

For new high-energy density compounds, a series of new bicyclo[2.2.1]heptane derivatives were designed and studied by density functional theory (DFT) method. The heat of formation (HOF) was evaluated by the isodesmic reaction. The densities and the heats of sublimation were predicted by the electrostatic potential analysis at B3PW91/6-31G(d,p) and B3LYP/6-311++G(2df,2p) levels, respectively. The detonation performances were predicted by the Kamlet-Jacobs equations. The bond dissociation energies (BDE) and impact sensitivity that is evaluated by the free space per molecule were also studied to give a better understanding of the stability. Results show that HOFs increase with the increasing number of N atoms. When the number of NO2 groups is larger than 4, HOFs generally increase with the increasing number of NO2 groups. Even though solid-phase HOF is decreasing, detonation energy is always rising with Oxygen Balance (OB) closing to zero-OB, and positive value of OB will largely reduce detonation energy. Detonation velocity and detonation pressure of the designed compounds are in the range of 5.62–9.46km/s and 11.72–41.44GPa, respectively. And detonation velocity and detonation pressure always increase with the increasing number of N atoms or NO2 groups except when OB is positive value. BDEs of all designed compounds are larger than 20kcal/mol shows that all designed compounds have a reasonable thermal stability. The calculated impact sensitivities show that all designed HEDCs have acceptable sensitivity. Especially impact sensitivity of C7, D7, E7, F6andG6 are expected to be very close to Tetryl (h50=25cm). Considering the thermal stability, impact sensitivity and detonation performance, A8, B8, C7, C8, D7, E7, F6andG6 might be interesting candidates for use as HEDCs.

Magnetic and Magnetocaloric Properties of High-Energy Ball-Milled Nanocrystalline CeMn2Ge2 Compound

CeMn2Ge2 nanopowders have been obtained by high-energy ball milling for 5 and 10 hours from bulk compound to investigate the effect of milling time on magnetic and magnetocaloric properties. CeMn2Ge2 nanopowders have been characterized by X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy, transmission electron microscopy, and magnetization measurements. The average grain size of the nanoparticles from XRD measurements is about 12.2 and 8 nm for 5-hour and 10-hour ball-milled samples, respectively. The investigations reveal that magnetic entropy change (∆S m) can be altered by changing the particle size of the compound. Maximum ∆S m is −2.45 and −1.30 J kg−1 K−1 for the 5- and 10-hour ball-milled nanopowders, respectively.

Synthesis of Tetrazino-tetrazine 1,3,6,8-Tetraoxide (TTTO).

This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6-e][1,2,3,4]tetrazine 1,3,6,8-tetraoxide (TTTO). It was synthesized in ten steps from 2,2-bis(tert-butyl-NNO-azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4-tetrazine 1,3-dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert-butyl-NNO-azoxy groups. The TTTO structure was confirmed by single-crystal X-ray.

Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO)

AbstractThis study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6‐e][1,2,3,4]tetrazine 1,3,6,8‐tetraoxide (TTTO). It was synthesized in ten steps from 2,2‐bis(tert‐butyl‐NNO‐azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4‐tetrazine 1,3‐dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert‐butyl‐NNO‐azoxy groups. The TTTO structure was confirmed by single‐crystal X‐ray.

Inverse Hall–Petch like behaviour in a mechanically milled nanocrystalline Al5Fe2 intermetallic phase

In the present investigation, the indentation study on the high-energy ball-milled nanocrystalline Al5Fe2 intermetallic compound has established the inverse Hall–Petch (IHP) behaviour. The structural characterisation of the milled powder particles by X-ray diffraction (XRD) and transmission electron microscopy has shown the evolution of nanocrystalline phase. Micro-indentation measurements have revealed the increase in hardness with decreasing grain size, reaching to a maximum of 9.0 ± 0.3 GPa up to a grain size of 32 ± 4 nm, followed by a decrease. The decrease in hardness with further refinement, an indication of grain size softening, demonstrates the IHP-like behaviour. The deviation from the Hall–Petch behaviour has been discussed using various models based on the dislocations and grain boundary-mediated processes. From the analysis, it appears that the model based on mesocopic grain boundary sliding phenomena is more appropriate to account for the observed grain size softening.

Collision Induced Loads in Pro-Injectors of ADDA Rocket Motors

The major improvement introduced by ADDA in space propulsion is the new Compound Rocket Motor concept (CRM), where, in contrast to the inefficient hybrid motors, the completion of combustion is very high. This new motor construction is also remarkable through its new injector type called pro-injector, currently under examination for patenting, with the capability of cutting out the dangerous reversed flow of the liquid component in a definitely short amount of time. The pro-injector device, quite critical when instable, high energy compounds like nitrous oxide are sprayed into the CRM combustion chamber, was designed, tested and successfully applied within the NERVA-ORVEAL project coordinated by the ADDA research team in cooperation with the AEROFINA partner. The results of the research regarding the pro-injector behavior are described. It was observed that unexpectedly high dynamic loads appear upon the seat of the pro-injector due to the collision-type motion when a shock wave in the combustion chamber develops. It is shown that such occurrence impedes application of fragile materials in the construction of the injector seat which otherwise would better serve the construction. Numerical simulations are presented as performed under rational assumptions regarding the mechanical behavior of mobile parts, in order to secure a smooth work of the device at the fast response required to downwind gas pressure shocks. The pro-injector proved being an innovative device currently submitted for patenting