Controlling the Energetic Properties of N-Methylene-C-Linked 4-Hydroxy-3,5-dinitropyrazole- and Tetrazole-Based Compounds via a Selective Mono- and Dicationic Salt Formation Strategy.

In the quest to synthesize high-performing insensitive high-energy density materials (HEDMs), the main challenge is establishing an equilibrium between energy and stability. For this purpose, we explored 4-hydroxy-3,5-dinitropyrazole- and tetrazole-based energetic scaffolds connected via a N-methylene-C bridge. The hydroxy functionality between nitro groups on the pyrazole ring promotes physical stability via inter- and intramolecular hydrogen bonding and contributes to oxygen balance, supporting better energetic performance. Due to two acidic sites (OH and NH) with different reactivities, a series of monocationic and dicationic salts were synthesized, and their overall performance was compared. All compounds synthesized in this study have high physical stability with impact sensitivity >40 J and friction sensitivity >360 N. Monocationic salts were generally found to have better thermal stability with respect to their corresponding dicationic energetic salts, which showed better energetic performance. The salt formation strategy effectively improved the thermal stability of 2 (Td = 168 °C), where most energetic salts have decomposition temperatures higher than 220 °C. All of the compounds were characterized through IR, multinuclear NMR spectroscopy, high-resolution mass spectrometry (HRMS), and elemental analysis. The structure-property relationship was studied using Hirshfeld surface analysis, noncovalent interaction (NCI) analysis, and electrostatic potential studies.

Design, characterization and evaluation of a new 99mTc-labeled folate derivative with affinity towards folate receptor.

Folate receptors (FRs) are known to be over-expressed in several human malignancies and therefore serve as an important target for small radiolabeled folate derivatives for non-invasive imaging of tumor, which is an important tool for future treatment recourse. In the present article, we report the synthesis of a new 99mTc-labeled radiotracer for the aforementioned application following the well-established 99mTc-'4+1' chemistry. Formation of the desired [99mTc]Tc-complex with >95% radiochemical purity was confirmed by radio-HPLC and its structure was ascertained by characterizing a natural rhenium analogue of the said complex. Although the ligand exhibited a weaker affinity towards FRs compared to native folic acid (IC50 8.09 µM vs 29.46 nM), the 99mTc-labeled complex was found to bind folate receptor-positive KB cells with high specificity (∼90%). Similar studies in a folate receptor negative cell line viz. A549 further corroborated the receptor-specificity of the synthesized complex. In vivo studies in KB tumor xenograft showed moderate uptake of ∼2.6% upto 3 h post-injection with high specificity (∼80%). The favorable features observed warrant further screening of the current design towards achieving an improved molecular probe for the said application.

Polynitro-functionalized 4-phenyl-1H-pyrazoles as heat-resistant explosives.

A new class of heat-resistant explosives was synthesized by coupling N-methyl-3,5-dinitropyrazole with polynitrobenzene moieties through carbon-carbon bonds. Simple Pd(0)-based Suzuki cross-coupling reactions between N-methyl-4-bromo-3,5-dinitropyrazole and 4-chloro/3-hydroxy-phenylboronic acid followed by nitration, amination and oxidation lead to the formation of C-C connected penta-nitro energetic derivatives 6 and 10. Various other energetic derivatives, such as amino (5), azido (7), nitramino (8) and energetic salts (11-14), were also explored to fine-tune their properties. All the compounds were thoroughly characterized using IR, NMR [1H, 13C{1H}], differential scanning calorimetry (DSC), elemental analysis, and HRMS studies. Compounds 5, 10 and 13 were further characterized through 15N NMR, and the crystal structures of 6 and 14 were confirmed through single-crystal X-ray diffraction studies. The physicochemical and energetic properties of all the energetic compounds were explored. Most of the synthesized compounds demonstrated high thermal stability (decomposition temperature Tdec > 250 °C), among which compounds 5 and 6 showed excellent thermal stability, having decomposition temperatures above 300 °C. The excellent thermal stability, acceptable sensitivity and good energetic properties of compounds 5, 6, 10 and 13 make them promising heat-resistant explosives. Furthermore, these compounds were found to be more thermally stable than the known N-methyl-3,5-dinitropyrazole-based and C-N coupled 3,4,5-trinitrobenzene-azole-based energetic compounds.

Valorised polypropylene waste based reversible sensor for copper ion detection in blood and water.

Heavy metals and plastic pollutants are the two most disastrous challenges to the environment requiring immediate actions. In this work, a techno-commercially feasible approach to address both challenges is presented, where a waste polypropylene (PP) based reversible sensor is produced to selectively detect copper ions (Cu2+) in blood and water from different sources. The waste PP-based sensor was fabricated in the form of an emulsion-templated porous scaffold decorated with benzothiazolinium spiropyran (BTS), which produced a reddish colour upon exposure to Cu2+. The presence of Cu2+ was checked by naked eye, UV-Vis spectroscopy, and DC (Direct Current) probe station by measuring the current where the sensor's performance remained unaffected while analysing blood, water from different sources, and acidic or basic environment. The sensor exhibited 1.3 ppm as the limit of detection value in agreement with the WHO recommendations. The reversible nature of the sensor was determined by cyclic exposure of the sensor towards visible light turning it from coloured to colourless within 5 min and regenerated the sensor for the subsequent analysis. The reversibility of the sensor through exchange between Cu2+- Cu+ was confirmed by XPS analysis. A resettable and multi-readout INHIBIT logic gate was proposed for the sensor using Cu2+ and visible light as the inputs and colour change, reflectance band and current as the output. The cost-effective sensor enabled rapid detection of the presence of Cu2+ in both water and complex biological samples such as blood. While the approach developed in this study provides a unique opportunity to address the environmental burden of plastic waste management, it also allows for the possible valorization of plastics for use in enormous value-added applications.

Vegetation health conditions assessment and mapping using AVIRIS-NG hyperspectral and field spectroscopy data for -environmental impact assessment in coal mining sites.

This paper focuses on vegetation health conditions (VHC) assessment and mapping using high resolution airborne hyperspectral AVIRIS-NG imagery and validated with field spectroscopy-based vegetation spectral data. It also quantified the effect of mining on vegetation health for geo-environmental impact assessment at a fine level scale. In this study, we have developed and modified vegetation indices (VIs) based model for VHC assessment and mapping in coal mining sites. We have used thirty narrow banded VIs based on the statistical measurement for suitable VIs identification. The highest Pearson's r, R2, lowest RMSE, and P values indices have been used for VIs combined pixels analysis. The highest different (Healthy vs. unhealthy) vegetation combination index (VCI) has been selected for VHC assessment and mapping. We have also compared VIs model-based VHC results to ENVI (software) forest health tool and Spectral-based SAM classification results. The 1st VCI result showed the highest difference (72.07%) from other VCI. The AUC values of the ROC curve have shown a better fit for the VIs model (0.79) than Spectral classification (0.74), and ENVI FHT (0.68) based on VHC results. The VHC results showed that unhealthy vegetation classes are located at low distances from mine sites, and healthy vegetation classes are situated at high distances. It is also seen that there is a highly significant positive relationship (R2 =0.70) between VHC classes and distance from mines. These results will provide a guideline for geo-environmental impact assessment in coal mining sites.

A visual review of artificial intelligence and Industry 4.0 in healthcare.

The COVID-19 outbreak has led to a substantial loss of human life throughout the world and has a tremendous impact on healthcare services. Industry 4.0 technologies have established effective supply chain management towards the fulfillment of customized demands in the healthcare field. In addition, the internet of things, artificial intelligence, big data analytics, and 3D printing have been extensively used to combat the COVID-19 pandemic and assist in providing value-added services in the healthcare sector. Henceforth, this paper presents a scientometric analysis on the literature of aforementioned Industry 4.0 technologies in the context of COVID-19. It provides extensive insights into co-citation and co-occurrence analysis of high cited publications, participating countries, influential authors, prolific journals, and keywords using the CiteSpace tool. The analyses reveal that China has produced the highest research outputs, although India is the most collaborative country in this field. The current research hotspots include supply chain, 4D printing, and social distancing technologies. Furthermore, it explores emerging trends, intellectual structure of publications, research frontiers, and potential research directions for further work in the Industry 4.0 assisted healthcare domain.

Many-Body Chaos in Thermalized Fluids.

Linking thermodynamic variables like temperature T and the measure of chaos, the Lyapunov exponents λ, is a question of fundamental importance in many-body systems. By using nonlinear fluid equations in one and three dimensions, we show that in thermalized flows λ∝sqrt[T], in agreement with results from frustrated spin systems. This suggests an underlying universality and provides evidence for recent conjectures on the thermal scaling of λ. We also reconcile seemingly disparate effects-equilibration on one hand and pushing systems out of equilibrium on the other-of many-body chaos by relating λ to T through the dynamical structures of the flow.

Hierarchical PANI/ZnO nanocomposite: synthesis and synergistic effect of shape-selective ZnO nanoflowers and polyaniline sensitization for efficient photocatalytic dye degradation and photoelectrochemical water splitting.

Hierarchical nanoflowers (NFs) of zinc oxide (ZnO) have been synthesized in the hexagonal wurtzite structure by a facile hydrothermal method. Polyaniline (PANI) has been prepared by the chemical oxidative polymerization method and incorporated with ZnO NFs by the chemisorption method. The potential of the synthesized nanostructures has been demonstrated for efficient photocatalytic degradation of methylene blue (MB) and photoelectrochemical water splitting. The PANI/ZnO nanocomposite has exhibited the enhanced photocatalytic activity which is ∼9 fold higher in comparison to pristine ZnO NFs and enhanced photocurrent density which is ∼16 fold higher than the ZnO photoanode. Importantly, ∼4 fold increment in the incident photon-to-current conversion efficiency (IPCE) is exhibited by PANI/ZnO, than that of ZnO photoanode. The remarkably enhanced photocatalytic and photoelectrochemical performance of PANI/ZnO nanocomposite is attributed to the availability of more interfacial sites facilitated by the hierarchical ZnO NFs, improved overall photoresponse due to its photosensitization with PANI and the resulting type-II heterojunction between them, which helps in the efficient separation of photogenerated charge carriers at the interface. A plausible reaction mechanism for the substantially improved performance of nanostructured PANI/ZnO towards MB degradation and water splitting has also been elucidated.

Enhanced photoelectrochemical performance of NaNbO3 nanofiber photoanodes coupled with visible light active g-C3N4 nanosheets for water splitting.

Sodium niobate nanofibers (NaNbO3-NF) have been synthesized using a hydrothermal technique and further coupled with visible light responsive graphitic carbon nitride (g-C3N4) nanosheets in different concentration ratios of 2:1 (2-CN), 4:1 (4-CN) and 8:1 (8-CN). A significant improvement in the photoelectrochemical (PEC) performance of the g-C3N4/NaNbO3-NF (4-CN) nanostructured photoanode compared to the bare NaNbO3 photoanode is observed. A current density of 12.55 mA cm-2 at 1 V with respect to the Ag/AgCl reference electrode is achieved for the g-C3N4/NaNbO3-NF (4-CN) photoanode, which is ∼3 times higher than the NaNbO3-NF photoanode. Also, compared to NaNbO3-NF, the g-C3N4/NaNbO3-NF (4-CN) nanocomposite photoanode showed ∼3 times improvement in the incident photon-to-current conversion efficiency. The improvement in the PEC performance of visible light active g-C3N4/NaNbO3-NF (4-CN) nanocomposite is attributed to the improved photoresponse of NaNbO3-NF due to the coupling of g-C3N4 and the formation of a type-II heterojunction between them leading to the enhanced separation of the photogenerated charge carriers. A possible reaction mechanism for the improved PEC water splitting performance has been proposed for the g-C3N4/NaNbO3-NF (4-CN) photoanode.

Bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)methanone: An Applicable and Very Dense Green Oxidizer.

Ammonium perchlorate (AP) is most often used as a practical solid rocket propellant because of its excellent performance. However, AP has many shortcomings, including instability, high negative enthalpy of formation, and claimed health and environmental issues resulting from its combustion products. The pursuit of highly dense, high-performance, and environmentally friendly oxidizers as solid propellants has long attracted scientists around the world. In this work, bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)methanone (3) was obtained from bis(3-nitro-1H-1,2,4-triazol-5-yl)methane (1) with chloroacetone followed by nitration. The structure of 3 was confirmed by elemental analysis and single-crystal X-ray diffraction. By introducing the carbonyl moiety, the density of 3 was increased to 1.945 g/cm3 and the decomposition temperature increased to 164 °C. Compound 3 is a green energetic oxidizer that has a positive oxygen balance (+8.7%), a high specific impulse (218 s), and an acceptable sensitivity (9 J, 240 N), making it a practical replacement for AP in solid rocket propellant formulations.

Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane.

Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material-3,7-diamino-2,6-dinitro-1H,5H-pyrazolo-[1,2-a]pyrazole-1,5-dione (4), the structure of which was comprehensively analyzed by a variety of advanced spectroscopic methods and by X-ray crystallo-graphy (with density of 1.845 g·cm-3 at 173 K). Although obtained crystals of 4 contained solvent molecules in their structure, state-of-the-art density functional theory (DFT) computational techniques allowed us to predict that solvent-free crystals of this explosive would preserve a similar tightly packed planar layered molecular arrangement, with the same number of molecules of 4 per unit cell, but with a smaller unit cell volume and therefore higher energy density. Explosive 4 was found to be heat resistant, with an onset decomposition temperature of 328.8 °C, and was calculated to exhibit velocity of detonation in a range of 6.88-7.14 km·s-1 and detonation pressure in the range of 19.14-22.04 GPa, using for comparison both HASEM and the EXPLO 5 software. Our results indicate that the trans-bimane explosophore could be a viable platform for the development of new thermostable energetic materials.

Multipurpose Energetic Materials by Shuffling Nitro Groups on a 3,3'-Bipyrazole Moiety.

A family of 3,3'-bipyrazole-based energetic compounds having C-NO2 /N-NO2 functionalities was synthesized by using various nitrating conditions. These nitro derivatives of bipyrazole are significantly more dense and energetic compared to the corresponding nitropyrazole analogues while maintaining the desired thermal stability and sensitivity. Depending on the number and nature of energetic nitro groups (C-NO2 /N-NO2 ), different classes of energetic materials, such as green primary explosives, high-performance secondary explosives and heat-resistant explosives, were obtained. All the compounds were thoroughly characterized by IR, NMR [1 H, 13 C{1 H}, 15 N], elemental analysis, and differential scanning calorimetry (DSC). Four were also structurally characterized with single-crystal X-ray diffraction studies. Heats of formation and detonation performance were calculated using Gaussian 03 and EXPLO5 v6.01 programs, respectively.

Balancing Excellent Performance and High Thermal Stability in a Dinitropyrazole Fused 1,2,3,4-Tetrazine.

The key to successfully designing high-performance and insensitive energetic compounds for practical applications is through adjusting the molecular organization including both fuel and oxidizer. Now a superior hydrogen-free 5/6/5 fused ring energetic material, 1,2,9,10-tetranitrodipyrazolo[1,5-d:5',1'-f][1,2,3,4]tetrazine (6) obtained from 4,4',5,5'-tetranitro-2H,2'H-3,3'-bipyrazole (4) by N-amination and N-azo coupling reactions is described. The structures of 5 and 6 were confirmed by single crystal X-ray diffraction measurements. Compound 6 has a remarkable room temperature experimental density of 1.955 g cm-3 and shows excellent detonation performance. In addition, it has a high decomposition temperature of 233 °C. These fascinating properties, which are comparable to those of CL-20, make it very attractive in high performance applications.

A Highly Stable and Insensitive Fused Triazolo-Triazine Explosive (TTX).

A fused-ring conjugated energetic molecule, 4-amino-3,7-dinitro-[1,2,4]triazolo[5,1-c] [1,2,4]triazine (TTX), has been synthesized in good yield in a two-step process starting from the known 5-amino-3-nitro-1H-1,2,4-triazole (ANTA). Characterization of TTX shows that it possesses energetic properties approaching those of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but with a higher thermal stability and lower sensitivity towards impact and friction.

N-Acetonitrile Functionalized Nitropyrazoles: Precursors to Insensitive Asymmetric N-Methylene-C Linked Azoles.

Properties of energetic compounds obtained by linking energetic pyrazoles to tetrazoles by means of N-methylene-C bridges can be fine-tuned. Reactions of pyrazole derivatives with chloroacetonitrile followed by conversion of the cyano group to tetrazole using click reactions in the presence of zinc chloride result in asymmetric N-methylene-C bridged azole-based energetic compounds. All the compounds were thoroughly characterized by IR and NMR [1 H, 13 C {1 H}, 15 N] spectroscopy, elemental analysis, and differential scanning calorimetry (DSC), and for two compounds, further supported by single-crystal X-ray diffraction studies. Heats of formation and detonation performances were calculated using Gaussian 03 and EXPLO5 v6.01 programs, respectively. Initial studies show that this new approach is promising for synthesizing less sensitive energetic compounds with fine-tuned properties.

New Generation Agent Defeat Weapons: Energetic N,N'-Ethylene-Bridged Polyiodoazoles.

Sodium salts of iodine-rich pyrazole and imidazole with 1-(2-bromoethyl)-5-aminotetrazole are useful precursors for energetic N,N'-ethylene-bridged polyiodoazoles. Compounds 1-3 were characterized with IR, and 1 H and 13 C NMR spectroscopy as well as elemental analyses. The molecular structures of 1 and 2 were confirmed by using single crystal X-ray diffraction. Heats of formation were calculated using Gaussian 03 and detonation properties and biocidal efficiency were calculated with CHEETAH 7. The decomposition products of 1-3 destroy microbes more effectively than some previously reported biocides since the thermal decomposition occurs at below 400 °C without addition of oxidizer or combustion adjuvant.

Reactions of alkyne- and butadiyne-derived fluorinated cyclophosphazenes with diiron and dimolybdenum carbonyls.

The reaction of (ß-phenylethynyl)pentafluorocyclotriphosphazene, [(PhC≡C)(F)PN](PNF2)2, with Fe2(CO)9 in refluxing hexane resulted in five new compounds, namely, [Fe(CO)2{η(2):η(2)-2,4-(P3N3F5)2Ph2C4Fe(CO)3}-µ-CO] (1), [Fe(CO)2{η(2):η(2)-2,5-(P3N3F5)2Ph2C4Fe(CO)3}-µ-CO] (2), [Fe(CO)2{η(5)-2,5-(P3N3F5)2Ph2C4CO}C(Ph)═C(P3N3F5)](3), [Fe(CO)3{η(2):η(2)-2,4-(P3N3F5)2Ph2C4CO] (4), and [Fe(CO)3{η(2):η(2)-2,5-(P3N3F5)2Ph2C4CO] (5). While compounds 1, 2, 4, and 5 have five-membered ferracyclopentadiene or cyclopentadienone rings coordinated to the Fe(CO)3 unit in the η(2):η(2) mode, compound 3 has a 2,5-cyclopentadienone ring attached to an Fe(CO)2(P3N3F5)C═C(Ph) unit, where Fe is η(5)-bonded to the cyclopentadienone ring, and the carbon that is α to the phenyl unit of the Fe(CO)2(P3N3F5)C═C(Ph) group is σ-bonded to the oxygen atom of the cyclopentadienone ring. Formation of five-membered cyclic compounds having two fluorophosphazene units on the vicinal carbon atoms of C4R2R'2Y rings was not observed in this reaction. No examples of Fe(CO)3-bound cyclobutadiene complexes were also isolated from this reaction. A similar reaction in the presence of trimethylamine N-oxide, NMe3O, was found to proceed at -20 °C with the formation of compounds 4 and 5 only. In contrast to the Fe2(CO)9 reaction, a reaction of alkyne-derived pentafluorocyclotriphosphazenes, [(RC≡C)(F)PN](PNF2)2 [R = Ph, Fe(C5H5)2] with the molybdenum complex Cp(CO)3Mo-Mo(CO)3Cp (Cp = cyclopentadienyl) in refluxing toluene resulted in the simple tetrahedral clusters Cp(CO)2Mo(P3N3F5)C-C(Ph)Mo(CO)2Cp (6) and Cp(CO)2Mo(P3N3F5)C-C(Fc)Mo(CO)2Cp (7) (Fc = ferrocenyl). A similar reaction of Cp(CO)3Mo-Mo(CO)3Cp with butadiyne-derived fluorophosphazenes, [(RC≡C-C≡C)(F)PN](PNF2)2 [R = Ph, Fe(C5H5)2], yielded the tetrahedral clusters Cp(CO)2Mo(P3N3F5)C-C(C≡CPh)Mo(CO)2Cp (8) and Cp(CO)2Mo(P3N3F5)C-C(C≡CFc)Mo(CO)2Cp (9) with the tetrahedral Mo2C2 unit forming exclusively with the alkyne unit of the butadiyne group bound to the cyclophosphazene ring. The crystal structures and infrared spectral data of these molybdenum clusters showed the presence of a semibridging carbonyl on one of the molybdenum units. All new compounds were characterized by IR, NMR [(1)H, (13)C{(1)H}, (31)P{(1)H}, and (19)F{(1)H}] and high-resolution mass spectrometry studies. Compounds 2, 3, 5, and 7-9 were also structurally characterized using single-crystal X-ray diffraction studies.

Optimizing coal mine planning and design for sustainable development in the context of mass exploitation of coal deposits.

Sustainable mining practices is a concept that embeds the principles of sustainable development into the whole mine life-cycle, from exploration, extraction and processing through to mine closure. The optimization of coal mine planning and the developing a standardized design for its sustainable development is very challenging and requires more effort. The present research attempts to address the conditions of sustainability and necessary measures for sustainable development, thereby providing appropriate solutions for each stage of mining operation besides expressing the necessity of sustainable development integration at different stages of mining life cycle (MLC). The approach of systems engineering is essential to assist the sustainability goals which are integrated with the expected results. Hence a method depending more on systems engineering principles and optimization can be incorporated to attain better results. Several socio-environmental factors associated with sustainability depends on the geographic condition and few mining engineering considerations such as mine location, topography, coal seam characteristics and so on. These systems engineering approach can be further enhanced by incorporating tools like Geographic Information System (GIS), which provides more accuracy and precision of the geographic conditions of the site identified for the coal mining plan. In order to begin this way of approach towards the sustainability development and mining planning, the appropriate optimization parameters should be identified. The outcome of these optimization parameters can be also achieved by optimizing coal mining system models.

Zwitterionic Energetic Materials: Synthesis, Structural Diversity and Energetic Properties.

Zwitterionic compounds are an emergent class of energetic materials and have gained synthetic interest of many in the recent years. Due to their better packing efficiencies and strong inter/intramolecular electrostatic interactions, they often ensue superior energetic properties than their salt analogues. A systematic review from the perspective of design, synthesis, and physicochemical properties evaluation of the zwitterionic energetic materials is presented. Depending on the parent ring(s) used for the synthesis and the type of moieties bearing positive and negative charges, different classes of energetic materials, such as primary explosives, secondary explosives, heat resistant explosives, oxidizers, etc., may result. The properties of some of the energetic zwitterionic compounds are also compared with analogous energetic salts. This review will encourage readers to explore the possibility of designing new zwitterionic energetic materials.

Pushing the Limit of Oxygen Balance on a Benzofuroxan Framework: K2DNDP as an Extremely Dense and Thermally Stable Material as a Substitute for Lead Azide.

Because of environmental and health impacts, there is an ongoing necessity to develop sustainable primary explosives to replace existing lead-based analogues. Now we describe a potential primary explosive, dipotassium 4,6-dinitro-5,7-dioxidobenzo[c][1,2,5]oxadiazole 1-oxide (K2DNDP), which exhibits an excellent thermal stability (Tdec = 281 °C), positive oxygen balance (+4.79%), and a calculated crystal density of ρ = 2.274 g cm-3 at 100 K. Its physicochemical properties concomitantly with its straightforward synthesis make it a potential replacement for lead-based initiators.