Synthesis and Study of Steering of Azido-tetrazole Behavior in Tetrazolo[1,5-c]pyrimidin-5-amine-Based Energetic Materials.

Tetrazoles and their derivatives are essential for compound synthesis due to their versatility, effectiveness, stability in air, and cost-efficiency. This has stimulated interest in developing techniques for their production. In this work, four compounds, tetrazolo[1,5-c]pyrimidin-5-amine (1), N-(4-azidopyrimidin-2-yl)nitramide (2), tetrazolo[1,5-c]pyrimidin-5(6H)-one (3), and tetrazolo[1,5-a]pyrimidin-5-amine (4), were obtained from commercially available reagents and straightforward synthetic methodologies. These new compounds were characterized by infrared (IR), 13C, and 1H NMR spectroscopy, differential scanning calorimetry (DSC), and single-crystal X-ray diffraction. The solvent, temperature, and electron-donating group (EDG) factors that were responsible for the steering of azido-tetrazole equilibrium in all compounds were also studied. In addition, the detonation performance of the target compounds was calculated by using heats of formation (HOFs) and crystal densities. Hirshfeld surface analysis was used to examine the intermolecular interactions of the four synthesized compounds. The results show that the excellent properties of 1-4 are triggered by ionic bonds, hydrogen bonds, and π-π stacking interactions, indicating that these compounds have the potential to be used in the development of high-performance energetic materials. Additionally, DFT analysis is in support of experimental results, which proved the effect of different factors that can influence the azido-tetrazole equilibrium in the synthesized pyrimidine derivatives in the solution.

Nitrogen-vacancy-rich molybdenum nitride nanosheets as highly efficient electrocatalysts for nitrogen reduction reaction.

The development of low-cost earth-abundant electrocatalysts to produce ammonia (NH3) with high efficiency for the nitrogen (N2) reduction reaction (NRR) remains challenging. Herein, we propose the development of highly efficient ultrathin nitrogen-vacancy-rich molybdenum nitride nanosheets (MoN-NV) for NRR using basic electrolytes under ambient conditions. In 0.1 M KOH, this catalyst attained a high faradaic efficiency (FE) of ∼14% with an NH3 yield of 22.5 µg h-1 mg-1cat at -0.3 V vs. a reversible hydrogen electrode under ambient conditions. The characterization results and electrochemical studies disclosed that nitrogen vacancies in the MoN-NV nanosheets played a critical role in the enhanced electrocatalytic activity for NRR. Furthermore, the recycling tests confirmed the stability of the catalyst during NRR electrolysis.

Nanosheet arrays of iron oxide for enhanced ammonia synthesis via electrochemical nitrogen reduction for prospective algal membrane bioreactors.

The earth's nitrogen cycle relies on the effective conversion of nitrogen (N2) to ammonia (NH3). As a result, the research and development of catalysts that are earth-abundant, inexpensive, and highly efficient but do not need precious metals is of the utmost significance. In this investigation, we present a controlled synthesis technique to the fabrication of an iron oxide (Fe2O3) nanosheet array by annealing at temperatures ranging from 350 to 550 °C. This array will be used for the electrochemical reduction of atmospheric N2 to NH3 in electrolytes. The Fe2O3 nanosheet array that was produced as a result displays outstanding electrochemical performance as well as remarkable stability. When compared to a hydrogen electrode working under normal temperature and pressure conditions, the Fe2O3 nanosheet array produces an impressive NH3 production rate of 18.04 g per hour per mg of catalytically active material in 0.1 M KOH electrolyte, exhibiting an enhanced Faradaic efficiency (FE) of 13.5% at -0.35 V. This is accomplished by exhibiting an enhanced Faradaic efficiency (FE) of 0.1 M KOH electrolyte. The results of experiments and electrochemical studies reveal that the existence of cation defects in the Fe2O3 nanosheets plays an essential part in the enhancement of the electrocatalytic activity that takes place during nitrogen reduction reactions (NRR). This study not only contributes to the expanding family of transition-metal-based catalysts with increased electrocatalytic activity for NRR, but it also represents a substantial breakthrough in the design of catalysts that are based on transition metals, so it's a win-win. In addition, the use of Fe2O3 nanosheets as electrocatalysts has a lot of potential in algal membrane bioreactors because it makes nitrogen fixation easier, it encourages algae growth, and it makes nitrogen cycling more resource-efficient.

Efficient mineralization of sulfanilamide over oxygen vacancy-rich NiFe-LDH nanosheets array during electro-fenton process.

Electrochemical degradation of toxic sulfanilamide with inexpensive approach is in urgent demand due to the harmful effects of sulfanilamide for both humans and aquatic environments. Here, we reported an efficient mineralization of sulfanilamide by using NiFe-layered double hydroxide (NiFe-LDH) nanosheets array with abundant oxygen vacancies that was in situ grown on exfoliated graphene (EG) by a simple hydrothermal treatment at different temperatures. The hydrothermal temperature was carefully analyzed for control synthesis of oxygen vacancy-rich NiFe-LDH/EG nanosheets array (NiFe-LDH/EG-OVr) for sulfanilamide degradation. Owing to the abundant oxygen vacancies, NiFe-LDH/EG-OVr rapidly generated hydrogen peroxide (H2O2) and hydroxyl radical (•OH) during electro-Fenton (EF) process, which resulted in the 98% mineralization of sulfanilamide in first 80 min. The radicals trapping experiments revealed that the •OH radicals was participated as the main active oxidation species in the efficient mineralization of sulfanilamide. The present results indicated that the oxidative attack by •OH radicals initiated the degradation process of sulfanilamide. During the total degradation of sulfanilamide, several organic compounds including aminophenol, hydroquinone, and oxalic acid, were identified as main intermediates by using gas chromatography-mass spectroscopy (GC-MS) and high-performance liquid chromatography-mass spectroscopy (HPLC-MS).

Low Power Single Laser Activated Synergistic Cancer Phototherapy Using Photosensitizer Functionalized Dual Plasmonic Photothermal Nanoagents.

Combination therapy, especially photodynamic/photothermal therapy (PDT/PTT), has shown promising applications in cancer therapy. However, sequential irradiation by two different laser sources and even the utilization of single high-power laser to induce either combined PDT/PTT or individual PTT will be subjected to prolonged treatment time, complicated treatment process, and potential skin burns. Thus, low power single laser activatable combined PDT/PTT is still a formidable challenge. Herein, we propose an effective strategy to achieve synergistic cancer phototherapy under low power single laser irradiation for short duration. By taking advantage of dual plasmonic PTT nanoagents (AuNRs/MoS2), a significant increase in temperature up to 60 °C with an overall photothermal conversion efficiency (PCE) of 68.8% was achieved within 5 min under very low power (0.2 W/cm2) NIR laser irradiation. The enhanced PCE and PTT performance is attributed to the synergistic plasmonic PTT effect (PPTT) of dual plasmonic nanoagents, promoting simultaneous release (85%) of electrostatically bonded indocyanine green (ICG) to induce PDT effects, offering simultaneous PDT/synergistic PPTT. Both in vitro and in vivo investigations reveal complete cell/tumor eradication, implying that simultaneous PDT/synergistic PPTT effects induced by AuNRs/MoS2-ICG are much superior over individual PDT or synergistic PPTT. Notably, synergistic PPTT induced by dual plasmonic nanoagents also demonstrates higher in vivo antitumor efficacy than either individual PDT or PTT agents. Taken together, under single laser activation with low power density, the proposed strategy of simultaneous PDT/synergistic PPTT effectively reduces the treatment time, achieves high therapeutic index, and offers safe treatment option, which may serve as a platform to develop safer and clinically translatable approaches for accelerating cancer therapeutics.

Evaluation of cytotoxicity, hemocompatibility and spectral studies of chitosan assisted polyurethanes prepared with various diisocyanates.

In this research work cytocompatibility, mutagenicity, and hemolytic activity of chitosan-based polyurethanes (PUs) have been evaluated. The chitosan modified PUs were prepared by step-growth polymerization technique using various diisocyanates like isophorone diisocyanate (IPDI). 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), 2,4-toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) by reacting with hydroxyl-terminated polybutadiene (HTPB). Structural confirmation of prepared samples was done by FTIR-ATR and 1H NMR techniques. Chitosan bearing PU samples showed good hemocompatibility, non-mutagenic behavior and less or non-cytotoxic behavior with all the diisocyanates. Among all the diisocyanates, aromatic diisocyanate (TDI) showed less hemocompatibility, high mutagenicity, and more cytotoxicity. However, this still showed a better result than non-chitosan based sample. It is concluded that chitosan improved the biological behavior of PU samples.

Porous SnO2 nanoparticles based ion chromatographic determination of non-fluorescent antibiotic (chloramphenicol) in complex samples.

Nowadays, there are rising concerns about the extensive use of the antibiotics such as chloramphenicol (CAP), has threatened the human life in the form of various vicious diseases. The limited selectivity and sensitivity of confirmatory techniques (UV and electrochemical) and non-fluorescence property of CAP make its determination a challenging task in the modern pharmaceutical analysis. In order to redeem the selective, sensitive and cost-effective fluorescence methodology, here by the dual role of synthesized porous SnO2 nanoparticles were exploited; (i) a porous sorbent in a µ-QuEChERS based sample preparation and as (ii) a stimulant for the transformation of non-fluorescent analytes namely CAP and p-nitrophenol (p-NP) into their respective fluorescent product. We report a green, simple, selective and cost effective ion chromatographic method for CAP sensitive determination in three complex matrices including milk, human urine and serum. The synthesized sorbent not only selectively adsorbed and degraded the matrix/interferences but also selectively reduced the non-fluorescent antibiotic CAP into a fluorescent species. This developed ion chromatographic method exhibited good selectivity, linearity (r2 ≥ 0.996) and limit of detection (LOD) was in the range 0.0201-0.0280 µg/kg. The inter- and intraday precisions were also satisfactory having a relative standard deviation (RSDs) less than 14.96% and excellent recoveries of CAP in the range of 78.3-100.2% were retrieved in various complex samples.