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Nitrogen heterocyclic scaffolds retain their leading position as valuable building blocks in material science, particularly for the design of small-molecule energetic materials. However, the search for more balanced combinations of directly linked heterocyclic cores is far from being exhausted and aims to reach ideally balanced high-energy substances. Herein, we present the synthetic route to novel pyrazole-furoxan framework enriched with nitro groups and demonstrate a promising set of properties, viz., good thermal stability, acceptable mechanical sensitivity, and high detonation performance. In-depth crystal analysis showed that the isomers having lower-impact sensitivity values in both types of regioisomeric pairs are those with the exocyclic furoxan oxygen atom being closer to the pyrazole ring. Owing to the favorable combination of high crystal densities (1.83-1.93 g cm -3 ), positive oxygen balance to CO (up to +13.9%), and high enthalpies of formation (322-435 kJ mol -1 ), the synthesized compounds show high calculated detonation velocities (8.4-9.1 km s -1 ) and excellent metal accelerating abilities. The incorporation of the 3-nitrofuroxan moiety increases the thermal stability (by ca. 20 °C) and decreases the mechanical sensitivity of target hybrid materials in both types of regioisomeric pairs. Simultaneously, the detonation performance of 3-nitrofuroxans is almost identical to that of 4-nitrofuroxans, highlighting the potential of the regioisomeric tunability in the future design of energetic materials.

A facile and efficient method for the regioselective [3 + 2] cycloaddition of 4-azidofuroxans to 1-dimethylamino-2-nitroethylene under p -TSA catalysis affording (4-nitro-1,2,3-triazolyl)furoxans was developed. This transformation is believed to proceed via eliminative azide-olefin cycloaddition resulting in its complete regioselectivity. The developed protocol has a broad substrate scope and enables a straightforward assembly of the 4-nitro-1,2,3-triazole motif. Moreover, synthesized (4-nitro-1,2,3-triazolyl)furoxans were found to be capable of NO release in a broad range of concentrations, thus providing a novel platform for future drug design and related biomedical applications of heterocyclic NO donors.

A regioselective approach toward the synthesis of a set of new (2-vinyltetrazolyl)furoxans as potential energetic monomers has been realized. All target energetic materials were thoroughly characterized by spectral and analytical methods. Moreover, crystal structures of two representative heterocyclic systems were studied by single-crystal X-ray diffraction. Prepared high-energy substances have high combined nitrogen-oxygen content (63-71 %), high enthalpies of formation and good detonation parameters (D: 6.7-7.8 km s -1 ; P: 18-28 GPa). Mechanical sensitivities of the synthesized vinyltetrazoles range these explosives from highly sensitive to completely insensitive. Using calculations of molecular electrostatic potentials (ESP), structural factors influencing the impact sensitivity were revealed. Overall, newly synthesized (2-vinyltetrazolyl)furoxans are of interest as promising energetic monomers due to the presence of the vinyl moiety and explosophoric heterocyclic combination, while their performance exceeds that of benchmark explosive TNT., (© 2022 Wiley‐VCH GmbH.)

Methods for the synthesis of two types of isomeric dispirocompounds based on imidazothiazolotriazine and pyrrolidineoxindole, differing in the structure of imidazothiazolotriazine fragment, namely, linear dispiro[imidazo[4,5- e ]thiazolo[3,2- b ][1,2,4]triazine-6,3'-pyrrolidine- 4',3″-indolines] and angular dispiro[imidazo[4,5- e ]thiazolo[2,3- c ][1,2,4]triazine-7,3'-pyrrolidine-4',3″-indolines] were proposed. The first method relies on a 1,3-dipolar cycloaddition of azomethine ylides generated in situ from paraformaldehyde and N-alkylglycine derivatives to the corresponding oxindolylidene derivatives of imidazothiazolotriazine. The cycloaddition leads to a mixture of two diastereomers resulted from anti - and syn -approaches of azomethine ylide in approximately a 1:1 ratio, which were separated by column chromatography. Another method consists in rearrangement of linear dispiro[imidazo[4,5- e ]thiazolo[3,2- b ][1,2,4]triazine-6,3'-pyrrolidine-4',3″-indolines] into hitherto unavailable angular dispiro[imidazo[4,5- e ]thiazolo[2,3- c ]-[1,2,4]triazine-7,3'-pyrrolidine-4',3″-indolines] upon treatment with KOH. It was found that the anti -diastereomer of linear type underwent rearrangement into the isomeric angular syn -diastereomer, while the rearrangement of the linear syn -diastereomer gave the angular anti -diastereomer.

Nitrogen-rich energetic materials comprised of a combination of several heterocyclic subunits retain their leading position in the field of materials science. In this regard, a preparation of novel high-energy materials with balanced set of physicochemical properties is highly desired. Herein, we report the synthesis of a new series of energetic salts incorporating a (1,2,4-triazolyl) furoxan core and complete evaluation of their energetic properties. All target energetic materials were well characterized with IR and multinuclear NMR spectroscopy and elemental analysis, while compound 6 was further characterized by single-crystal X-ray diffraction study. Prepared nitrogen-rich salts have high thermal stability (up to 232°C), good experimental densities (up to 1.80 g cm -3 ) and high positive enthalpies of formation (344-1,095 kJ mol -1 ). As a result, synthesized energetic salts have good detonation performance ( D = 7.0-8.4 km s -1 ; p = 22-32 GPa), while their sensitivities to impact and friction are quite low., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Larin, Pivkina, Ananyev, Khakimov and Fershtat.)

A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR ( 1 H, 13 C, 14 N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8-76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62-1.88 g cm -3 ), very high enthalpies of formation (846-1720 kJ mol -1 ), and, as a result, excellent detonation performance (detonation velocities 7.66-9.09 km s -1 and detonation pressures 25.0-37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN., (© 2021 Wiley-VCH GmbH.)

A series of energetic nitrogen-rich salts comprised of a 5-(trinitromethyl)tetrazolate anion and high-nitrogen cations was synthesized by simple and efficient chemical routes from readily available commercial reagents. These energetic materials were fully characterized by IR and multinuclear NMR ( 1 H, 13 C, 14 N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt containing the 3,6,7-triamino-7 H -[1,2,4]triazolo[4,3- b ][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit decent experimental densities (1.648-1.845 g cm -3 ) and positive enthalpies of formation (up to 725.5 kJ mol -1 ) and, as a result, superior detonation performance (detonation velocities 8.2-9.2 km s -1 and detonation pressures 28.5-37.8 GPa), which is comparable to or even exceeding those of commonly used booster explosive PETN. On the other hand, high mechanical sensitivity of several novel 5-(trinitromethyl)tetrazolate salts along with their high combined nitrogen-oxygen content (>81%) and excellent detonation performance render them environmentally friendly alternatives to lead-based primary explosives.

In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4'-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3'-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen-rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR ( 1 H, 13 C, 14 N, 15 N) spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Additionally, the structure of an energetic salt consisting of an azidotetrazolylfuroxan anion and a 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed by single-crystal X-ray diffraction. The synthesized compounds exhibit good experimental densities (1.57-1.71 g cm -3 ), very high enthalpies of formation (818-1363 kJ mol -1 ), and, as a result, excellent detonation performance (detonation velocities 7.54-8.26 kms -1 and detonation pressures 23.4-29.3 GPa). Most of the synthesized energetic salts have moderate sensitivity toward impact and friction, which makes them promising candidates for a variety of energetic applications. At the same time, three compounds have impact sensitivity on the primary explosives level (1.5-2.7 J). These results along with high detonation parameters and high nitrogen contents (66.0-70.2 %) indicate that these three compounds may serve as potential environmentally friendly alternatives to lead-based primary explosives., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Results analysis of 162 low anterior rectum resections, carried out in the hospital during 1999-2006 years on account of upper and medial rectal ampulla adenocarcinoma is presented in the article. Method of marking rectum resection distal border with use of optical coherent tomography was worked out and put into practice. Comparative evaluation of operation results with total and partial mesorectal cellular tissue removal was carried out. It is established that local recurrence has been indexed in 14.28% of patients undergoing anterior resection with maintenance of mesorectum part in 7.89% of patients undergoing mesorectumectomy. Indications for mobilization of left bend colon and one or another type of discharge ostomy were formulated. Measures for prediction and prophylaxis of anal incontinence after rectum resection and also the new method of small pelvis cavity intraoperative drainage were offered.

Positive results of combined surgeries in locally advanced cancer of the colon complicated with gastric fistula (3 patients) and duodenal fistula (1 patient) are presented. Effective treatment of these patients requires complex examination, good preoperative preparation, perfect anesthetic management, adequate operation and intensive postoperative (including antibacterial) therapy.

BACKGROUND: Anti-ischemic therapy with nitrovaasodilators as NO-donors is complicated by the induction of tolerance. When nitrovasodilators are metabolized to release NO there is a considerable coproduction of oxygen-derived radicals leading to a diminished cyclic GMP production and to impaired vasomotory responses. We analyzed in vivo the glyceroltrinitrate-induced generation of strong oxidative/nitrating compounds contributing to development of tolerance. METHODS AND RESULTS: In 16 patients we studied the urinary nitrotyrosine excretion during either (1) placebo control conditions, (2) 2-day nonintermittent transdermal nitroglycerin administration (0.4 mg/h), (3) 2-day nonintermittent glyceroltrinitrate administration (0.4 mg/h) along with a continuous infusion of vitamin C (55 µg/kg/min) as an antioxidant, or (4) with vitamin C but without glyceroltrinitrate (diminished urinary nitrotyrosine content of 34 +/- 18 µg/day observed). Glyceroltrinitrate administration augmented urinary nitrotyrosine from 56 +/- 24 (basal) to 186 +/- 32 µg/day (glyceroltrinitrate tolerance). Coadministration of vitamin C caused complete elimination of tolerance and a decrease in urinary nitrotyrosine to 130 +/- 28 µg/day. Glyceroltrinitrate-induced formation of oxidants was confirmed in vitro comparing glyceroltrinitrate-induced and peroxynitrite-induced tachyphylaxis in isolated perfused rabbit hearts and analyzing tolerance-induced inactivation of solbule guanylyl cyclase in cultured aortic smooth muscle cells. CONCLUSIONS: Augmented urinary nitrotyrosine excretion during glyceroltrinitrate administration reflects enhanced formation of peroxynitrite and of nitrotyrosine. Glyceroltrinitrate-induced tolerance is the result of oxidative stress and can be suppressed by additional antioxidant therapy aimed to prevent glyceroltrinitrate-induced formation and/or actions of peroxynitrite.